Fluorine-containing olefin, fluorine-containing polymer and thermoplastic resin composition prepared by using said polymer

ABSTRACT

To provide a fluorine-containing olefin represented, for example, by CH 2  ═CFCF 2  --R f   6  --(CH 2 ) k  --X 2  [wherein, X 2  is ##STR1## R f   6  is a fluorine-substituted fluorine-containing alkyl group having 1 to 40 carbon atoms or --OR f   7  --(Rf 7  is a fluorine-substituted fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-substituted fluorine-containing ether group having 3 to 50 carbon atoms), k is 0 or an integer of 1 to 6]; a fluorine-containing polymer with functional group which is prepared by polymerizing the above-mentioned olefin, has good affinity with various heat-resisting thermoplastic resins and is capable of forming homogeneous dispersion with the thermoplastic resin; and a thermoplastic resin composition comprising the above-mentioned fluorine-containing polymer with functional group and an aromatic polyester or the like as the heat-resisting thermoplastic resin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional application of U.S. Ser. No. 08/596,315, filed Feb.9, 1996, now U.S. Pat. No. 5,670,593, which was a U.S. national phaseapplication of International Application No. PCT/JP95/01103, filed Jun.5, 1995.

TECHNICAL FIELD

The present invention relates to a novel fluorine-containing polymerwith functional group, which has excellent affinity with variousheat-resisting thermoplastic resins and is capable of forminghomogeneously dispersed conditions.

Further the present invention relates to a novel fluorine-containingolefin with functional group, which can give a functional group to thefluorine-containing polymer.

Further the present invention relates to a thermoplastic resincomposition which has improved mechanical properties and chemicalproperties and comprises the above-mentioned fluorine-containing polymerwith functional group and a thermoplastic resin having a melting pointof crystal or glass transition temperature of not less than 150° C.

BACKGROUND ART

Crystalline heat-resisting thermoplastic resins (these have a meltingpoint of crystal of not less than 150° C.) such as polyacetal,polyamide, aromatic polyester, poly(arylene sulfide), polyketones,poly(ether ketones), polyamideimide and poly(ether nitrile) areexcellent in mechanical properties and moldability, and therefore areused for functional parts in the fields of automobiles, industrialmachineries, office automation equipments, electrical and electronicequipments and the like. However there is a market demand for higherchemical resistance and sliding property and in addition, since theseresins are generally brittle, enhancement in impact resistance isparticularly desired. Also non-crystalline heat-resisting thermoplasticresins (these have a glass transition temperature of not less than 150°C.) such as polycarbonate, poly(phenylene ether), polyarylate,polysulfone, poly(ether sulfone) and poly(ether imide) are widelyemployed for uses where their transparency, dimensional stability,impact resistance and the like are utilized, but generally have problemsof chemical resistance, solvent resistance and moldability.

From another aspect, fluorine-containing resins such aspolytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoro(alkylvinyl ether) copolymer (PFA), tetrafluoroethylene/hexafluoropropylenecopolymer (FEP), poly(vinylidene fluoride) (PVDF) andethylene/tetrafluoroethylene copolymer (ETFE) are excellent in thermalresistance, chemical resistance, solvent resistance, weather resistance,sliding property, flexibility, electrical properties and the like, andare widely used in the fields of automobiles, industrial machineries,office automation equipments, electrical and electronic equipments andthe like. However as compared with the crystalline heat-resistingthermoplastic resins, in many cases, the fluorine-containing resins areinferior in mechanical properties and physical heat resistance as shownby a deflection temperature under load, and also are inferior indimensional stability as compared with non-crystalline heat-resistingthermoplastic resins, and thus their application is limited.

In order to eliminate the drawbacks of the above-mentioned non-fluorinetype heat-resisting thermoplastic resins, attempts for preparing novelmaterials have been aggressively made by combining with afluorine-containing polymer (resinous and elastomeric ones are included)or, contrarily, by modifying the resinous fluorine-containing polymerwith a non-crystalline heat-resisting thermoplastic resin.

First, as an example of simple melt-blending by means of a kneader, forinstance, JP-A-202344/1982 discloses that a commercially availablefluorine-containing elastomer is added to poly(arylene sulfide) for thepurpose to improve impact resistance, crack resistance and strengthagainst thermal shock without impairing the characteristics ofpoly(arylene sulfide) such as thermal resistance and chemicalresistance. Also JP-A-165647/1989 and JP-A-110156/1990 disclose that apolymer forming an anisotropic melt, i.e. a liquid crystal polymer(aromatic polyester and the like) is added for the purpose to decrease acoefficient of linear expansion and further to improve mechanicalproperties and moldability without impairing weather resistance,chemical resistance, wear resistance and antisoil property of thefluorine-containing polymer such as PVDF. As examples of a blend of aliquid crystal polymer and PTFE, there are JP-B-5693/1992 andJP-A-230756/1988. JP-A-7850/1975 discloses that it is effective to blendPVDF for improving water absorption property and hygroscopicity ofpolyamide.

Further JP-A-23448/1985 discloses an example of improving mold-releaseproperty by incorporating a fluorine-containing polymer to an aromaticpolysulfone composition of which shrinkage from mold dimensions isreduced by adding fibrous reinforcing agents such as glass fibers andwollastonite and inorganic fillers such as talc and glass beads.

Also attempts to improve sliding property by mixing PTFE powder tovarious synthesized resins have been widely conducted.

However there is a problem that usually the fluorine-containing polymerhas poor affinity with other materials, because of a small surfaceenergy thereof. For that reason, when the fluorine-containing polymer ismelt-blended with other materials, there occurs a phase separation, andan interfacial adhesivity therebetween is substantially zero, and thusinterfacial adhesion failure is easy to occur. In addition, thefluorine-containing polymer is difficult to disperse into othermaterials during blending, which results in aggregation and makes itdifficult to sufficiently exhibit effects of adding thefluorine-containing polymer.

In order to resolve these drawbacks or enhance affinity between thedifferent polymers, there is often added a compatibilizing agent as athird component. JP-A-218446/1987 discloses a composition prepared byblending a thermoplastic fluorine-containing elastomer in order toimprove impact resistance of poly(arylene sulfide) without impairing itsflowability, and teaches that it is more effective to add a polymercontaining a fluorinated aliphatic group for improving the affinity.Also JP-A-62853/1991 discloses a method of adding, as a compatibilizingagent, a graft polymer comprising a vinyl polymer having epoxy group andmethyl methacrylate polymer or acrylonitrile/styrene copolymer whenblending poly(arylene sulfide) and a thermoplastic resin including PVDF.

Also claim 2 of the above-mentioned JP-A-165647/1989, JP-A-197551/1989and JP-A-263144/1989 disclose that it is more effective to add anacrylic polymer, poly(vinyl acetate) and poly(vinyl methyl ketone),respectively to the blend of PVDF and an anisotropic melt-formingpolymer as compared with simple blending.

In JP-A-11109/1989 there is described an example of using, as acompatibilizing agent for blending polyamide and PVDF, a block polymercomprising any one of N-vinylpyrrolidone or methyl (meth)acrylate andany one of an ethylenically unsaturated monomer, polycondensated monomeror lactum.

Also JP-A-98650/1989 and JP-A-110550/1989 disclose the use, as acompatibilizing agent when blending poly(phenylene ether) and afluorine-containing polymer such as PVDF, of a copolymer comprisingpolystyrene and an acrylic polymer by utilizing excellent affinities ofpoly(phenylene ether) with polystyrene and of PVDF with an acrylicpolymer.

However in JP-A-218446/1987, the effect of improvement in affinity isnot enough because the fluorinated aliphatic group in thecompatibilizing agent has a low degree of polymerization, i.e., not morethan 20 of carbon atoms. Also all the other patent publicationssubstantially direct to examples of using non-fluorine typecompatibilizing agents synthesized by utilizing the excellent affinitybetween the PVDF and the carbonyl group-containing polymer such as anacrylic polymer, and thus the fluorine-containing polymer is limited toPVDF. Also in the affinity improving method using such compatibilizingagents, since chemical resistance and thermal resistance of thecompatibilizing agents themselves are poorer than those of the maincomponent polymer, there is a problem that physical properties of moldedarticles are lowered.

There are also attempts to improve dispersibility of compositionscomprising fluorine-containing polymers and thermoplastic resins byso-called dynamic vulcanization. JP-A-185042/199 1 discloses that, whenblending a crosslinkable fluorine-containing elastomer and athermoplastic polymer having a melting point of crystal or glasstransition temperature of not less than 150° C., dispersibility of thefluorine-containing elastomer is improved to give a thermoplasticelastomer by conducting vulcanization of the fluorine-containingelastomer during melt-blending. Also in JP-A-172352/1991, finedispersion of fluorine-containing rubbers has been achieved by utilizingthe dynamic vulcanization method for improving impact resistance ofpoly(phenylene sulfide) with a fluorine-containing elastomer.

However in these dynamic vulcanization methods, since thefluorine-containing elastomer is vulcanized during melt-blending withother materials, impurities derived from a vulcanizing agent and otheradditives to be usually used for vulcanization remain in thecomposition, which makes the properties of molded articles such aschemical resistance lowered.

Also particularly because in a dynamically vulcanized compositioncomprising the thermoplastic resin and the fluorine-containingelastomer, the thermoplastic resin becomes a matrix, for example,chemical resistance of the composition is easy to be influenced bycharacteristics of the thermoplastic resin, and the effect of adding thefluorine-containing elastomer is not sufficiently obtained.

On the other hand, there are reports with respect to a compositioncomprising a fluorine-containing polymer with reactive functional group.JP-A-105062/1988, JP-A-254155/1988 and JP-A-264672/1988 discloseexamples of a blend of a matrix polymer with a fluorine-containingpolyether with functional group at its end(s), a polymer containingfunctional group and a polyfluoroalkyl group having 2 to 20 carbon atomsor a fluorine-containing elastomer with functional group. However,either of these examples is conducted in the way of letting twofunctional group-containing polymers disperse in the matrix polymer andreact with each other to form a network structure, and then physicallybond the network structure to the matrix polymer. Namely, the way doesnot directly utilize chemical affinity and reactivity with the matrixpolymer.

Therefore a combination of two or more functional groups which reactwith each other is necessary, and it is required to regulate theconditions where those functional groups give a network structure. Alsothe fluorine-containing polyether is usually obtainable as an oilysubstance and is expensive, and moreover the effect of addition islimited to improvement of lubricity of the matrix polymer. Further asthe polyfluoroalkyl-containing polymer, only ones having low molecularweight, which are difficult to be defined as polymer, are exemplified.

Also JP-A-112612/1993 discloses modified fluorohydrocarbon polymers towhich substituents such as vinyl, allyl, acrylate, alkoxysilane, amide,sulfonic acid salt, pyridine and carboxylic acid salt are introduced.There is also described that among these substituents, particularlyamide is further converted to amino and carboxylester being converted tocarboxyl, and thus it is possible to graft to an aromatic polyamide andaromatic polyester. Also it is mentioned that the graft polymers areused for blending with commercially available engineering polymers toimprove their surface characteristics, weather resistance, wearresistance and water absorption property.

However the substituents of these modified polymers are introduced bypolymer reaction wherein Y-R-Z which is a combination of a highlyreactive nucleophilic group Y (amino, oxy, thio) and the above-mentionedmodifying substituent Z being connected through a bonding segment R, isreacted with a double bond formed in the vinylidene polymer bydehydrofluorination of the polymer.

That is, because of polymer reaction, it is difficult to introduce thesubstituents uniformly, and for that reason, there occurs an irregulardistribution in the concentration of functional groups, and thus it isdifficult to obtain sufficient effect on dispersibility and affinity atthe time of blending with the thermoplastic resin.

Also at the time of introduction of the modifying substituents andhydrolysis of amide or carboxylester, there remains a reactive reagent,which results in lowering of thermal resistance and chemical resistance.Further since the bonding segment of the modifying reagent is ofhydrocarbon type, thermal resistance of the obtained polymer itself islowered at that portion and the polymer is decomposed when kneading withthe heat-resisting thermoplastic resin at high temperature to lower thephysical properties of the blended composition. Also the vinylidenepolymer, after the dehydrofluorination, is colored markedly and externalappearance of the molded article is impaired remarkably. Also in thismethod, the fluorine-containing polymer is limited to vinylidenefluoride polymers, and also introduction of hydroxyl group and glycidylgroup is difficult, and thus sufficient effects of enhancingdispersibility cannot be obtained in blending with an aromaticpolyester, polycarbonate and poly(phenylene sulfide). Further there isno detailed description as to examples of the composition blended withthe heat-resisting thermoplastic resin and the physical properties atthe time of blending.

JP-A-8 1159/1988 discloses that mechanical properties of a thermoplasticelastomer composition can be improved by modifying a fluorine-containingrubber with any one of carboxyl, hydroxyl or epoxy group when blending apoly(ether ester amide) and the fluorine-containing rubber.

However the described fluorine-containing rubber with functional groupis prepared by copolymerizing a fluorine-containing monomer and anacrylic monomer with functional group to introduce the functional group.Therefore, the thermal resistance and chemical resistance are loweredand physical properties of a molded article is lowered when blended withthe heat-resisting thermoplastic resin. The functional group-containingacrylic monomer has poor copolymerizability with a fluorine-containingmonomer represented by tetrafluoroethylene and vinylidene fluoride, anda uniform concentration of functional groups is difficult to obtain inevery polymer molecule, which results in an irregular distribution ofcomponents. Thus it is difficult to obtain sufficient effects ondispersibility and affinity in blending with the thermoplastic resin.Also poly(ether ester amide) is usually low in chemical resistance ascompared with polyamide.

As mentioned above, when blending a fluorine-containing polymer and athermoplastic resin, since the fluorine-containing polymer usually haspoor affinity, it is difficult to obtain a blend having stablecharacteristics, and physical properties of the molded article obtainedtherefrom is lowered. Also though various attempts have been made forimproving the affinity, such as study on additives and modification anddenaturation of the fluorine-containing resin, there have not beenobtained a fluorine-containing polymer and a composition prepared bymixing the fluorine-containing polymer and a thermoplastic resin, whichdo not lower thermal resistance and chemical resistance of thecomposition.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a novelfluorine-containing polymer with functional group, which has goodaffinity with various heat-resisting thermoplastic resins and is capableof forming homogeneous dispersed conditions, and a novelfluorine-containing olefin with functional group for preparation of thefluorine-containing polymer.

Further another object of the present invention is to provide athermoplastic resin composition which is improved in interfacialaffinity by blending the above-mentioned fluorine-containing polymerwith functional group and various heat-resisting thermoplastic resinsand can give excellent mechanical properties, moldability, thermalresistance and chemical resistance to molded articles.

DISCLOSURE OF THE INVENTION

The fluorine-containing olefin with functional group of the presentinvention is represented by the formula (IV):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.6 --(CH.sub.2).sub.k --X.sup.2 (IV)

wherein X² is ##STR2## R_(f) ⁶ is a fluorine-substituted alkylene grouphaving 1 to 40 carbon atoms or --OR_(f) ⁷ --(R_(f) ⁷ is afluorine-substituted fluorine-containing alkylene group having 1 to 40carbon atoms or a fluorine-substituted fluorine-containing ether grouphaving 3 to 50 carbon atoms), k is 0 or an integer of 1 to 6, orrepresented by the formula (V):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.8 --(CH.sub.2).sub.m --COOR.sup.4 (V)

wherein R⁴ is H, an alkyl group having 1 to 6 carbon atoms, Na, K, Li orNH₄, R_(f) ⁸ is a fluorine-substituted alkylene group having 3 to 40carbon atoms or --OR_(f) ⁹ --(R_(f) ⁹ is a fluorine-substituted alkylenegroup having 2 to 40 carbon atoms or a fluorine-substituted ether grouphaving 3 to 50 carbon atoms), m is 0 or an integer of 1 to 6.

The fluorine-containing polymer with functional group of the presentinvention is a copolymer of the following (A) and (B) and ischaracterized by comprising 0.01 to 80% by mole of (A) and 20 to 99.99%by mole of (B) and having a number average molecular weight of 2,000 to20,000,000.

(A) is one or more monomers represented by the formula (I):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.1 --(CH.sub.2).sub.a --X.sup.3 (I)

wherein X¹ is --CH₂ OH, --COOR¹ (R¹ is H, an alkyl group having 1 to 6carbon atoms, Na, K, Li or NH₄), ##STR3## R_(f) ¹ is afluorine-substituted alkylene group having 1 to 40 carbon atoms or--OR_(f) ² --(R_(f) ² is a fluorine-substituted alkylene group having 1to 40 carbon atoms or a fluorine-substituted ether group having 3 to 50carbon atoms), a is 0 or an integer of 1 to 6, and

(B) is one or more monomers selected from the group consisting ofmonomers represented by the formula (II): ##STR4## wherein Y¹ is F, Cλ,H or CF₃, Y² is F, Cλ, H, R_(f) ³ (R_(f) ³ is a perfluoroalkyl grouphaving 1 to 10 carbon atoms) or ##STR5## (b is 0 or an integer of 1 to5, R_(f) ⁴ is a perfluoroalkyl group having 1 to 6 carbon atoms) and theformula (III): ##STR6## wherein Z¹ is F, H, an alkyl group having 1 to 6carbon atoms or a perfluoroalkyl group having 1 to 10 carbon atoms, Z²is H, Cλ, an alkyl group having 1 to 6 carbon atoms or --(CF₂)_(d) --Z³(d is an integer of 1 to 10, Z³ is F or H).

The thermoplastic resin composition of the present invention comprises(D) 0.1 to 99% by weight of at least one selected from theabove-mentioned fluorine-containing polymers with functional group asthe fluorine-containing polymer with functional group and (E) 1 to 99.9%by weight of a heat-resisting thermoplastic resin having a melting pointof crystal or glass transition temperature of not less than 150° C.

The present inventions are explained below in order.

The first one of the present inventions relates to a novelfluorine-containing olefin with functional group, which can givehydroxyl, glycidyl, carboxyl or carboxylester to the fluorine-containingpolymer.

As a comonomer giving a similar functional group to the polymer, thereare most generally known (meth)acrylate or (meth)acrylic acid compoundswith hydroxyl, glycidyl and carboxyl, and vinyl ethers represented byhydroxyalkyl vinyl ether and glycidyl vinyl ether. Those hydrocarbontype unsaturated compounds with functional group have such drawbacksthat copolymerizability with fluoroolefins (olefins represented bytetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene andthe like) is insufficient and that even if the copolymerization ispossible, thermal resistance and chemical resistance of the obtainedcopolymer are lowered significantly.

On the other hand, as the fluorine-containing olefin with functionalgroup, in JP-A-54409/1988 there is reported a compound represented byCF₂ ═CF--(CF₂)₆₀ --(CH₂).sub.β --X (X is ##STR7## However because of itsinsufficient copolymerizability with fluoroolefins, the polymerizationrate is lowered and a large amount of the compound is necessary toobtain a copolymer having a desired composition.

JP-A-143888/1975 discloses a hemi-acetal compound represented by##STR8## wherein R is H or methyl, X' is F or Cλ, and JP-A-503 104/1993discloses a partly fluorine-substituted compound represented by CH₂═CH--Rf--CH₂ CH₂ Y, wherein Rf is a fluorine-substituted divalentorganic group, Y is CH₂ OH, COOH or others. Polymers prepared from thesemonomers have a drawback such that tertiary hydrogen like ##STR9## isyielded in trunk chains of the polymers, and thermal resistance of theobtained copolymer is lowered and particularly at high temperature,deterioration is easy to occur. Also the above-mentioned hemi-acetalcompound has a poor copolymerizability with a fluorine-containingmonomer, and particularly it is difficult to obtain a high molecularweight.

JP-A-85832/1983 and JP-A-503935/1993 disclose fluorine-containingolefins with hydroxyl and having a perfluoro(vinyl ether) group, andU.S. Pat. No. 4,209,635 discloses fluorine-containing olefins with acarboxylester group and having perfluoro(vinyl ether) group. A CF₂═CFO-- group in these fluorine-containing olefins has less resistance toalkaline medium. Particularly the fluorine-containing olefin withhydroxyl and having a perfluoro(vinyl ether) group may easily causecyclization of vinyl ether itself, homopolymerization reaction(fluorine-containing polyether is formed) and hydrolysis of the vinylether group under an environment of an acidity (for example, PKa is notless than 7) lower than that (PKa≈5 to 6) of hydroxyl group. Thereforefor instance, at the time of copolymerizing with other ethylenicallyunsaturated compounds in an aqueous medium, polymerization rate islowered under a weak alkaline to alkaline condition, and an amount ofvinyl ether to be introduced into the copolymer decreases. Therefore thepolymerization conditions cannot be selected from a wide range. Also amethod of synthesizing those perfluoro(vinyl ether) compounds withfunctional group is complicated and therefore such compounds areexpensive and economically disadvantageous in industrial scale.

An object of the present invention is to eliminate the above-mentioneddrawbacks and to provide a novel fluorine-containing olefin withfunctional group which is capable of endowing a fluorine-containingpolymer with functional groups. Specifically, according to the presentinvention there can be provided a novel fluorine-containing olefin whichcan introduce highly reactive functional groups into afluorine-containing polymer, and has the following characteristics.

1 Good copolymerizability with an ethylenically unsaturated compound,particularly an ethylenically unsaturated fluorine-containing compound.Thus a reaction rate is not lowered remarkably,

2 Not lowering thermal stability and chemical stability of the resultingcopolymer prepared by copolymerizing with the ethylenically unsaturatedfluorine-containing compound, and

3 Synthesis of the fluorine-containing olefin with functional group ofthe present invention being relatively easy and industriallyproduceable.

The first fluorine-containing olefin with functional group of thepresent invention is the fluorine-containing olefin which has hydroxylgroup or glycidyl group and is represented by the formula (IV):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.6 --(CH.sub.2).sub.k --X.sup.2 (IV)

wherein, X² is ##STR10## R_(f) ⁶ is a fluorine-substituted alkylenegroup having 1 to 40 carbon atoms or --OR_(f) ⁷ --(R_(f) ⁷ is afluorine-substituted alkylene group having 1 to 40 carbon atoms or afluorine-substituted ether group having 3 to 50 carbon atoms), k is 0 oran integer of 1 to 6.

In the fluorine-containing olefin of the formula (IV), one of thestructures of R_(f) ⁶ is a fluorine-substituted alkylene group having 1to 40 carbon atoms which includes a linear group, a branched group or amixture thereof.

A preferable typical example among those is the fluorine-containingolefin represented by the formula (1):

    CH.sub.2 ═CFCF.sub.2 --(CF.sub.2 CF.sub.2).sub.a' --(CH.sub.2).sub.b' --X.sup.3                                                 (1)

wherein X³ and b' are the same as the above-mentioned X² and k,respectively, a' is 0 or an integer of 1 to 10.

Further preferable typical examples are fluorine-containing olefinsrepresented by the formula (1-a):

    CH.sub.2 ═CFCF.sub.2 --CF.sub.2 --(CF.sub.2 CF.sub.2).sub.d' --(CH.sub.2).sub.e' --CH.sub.2 OH                         (1-a)

wherein d' is 0 or an integer of 1 to 10, e' is an integer of 1 to 5,the formula (1-b): ##STR11## wherein f' is 0 or an integer of 1 to 10,g' is 0 or an integer of 1 to 6, and the formula (1-c): ##STR12##wherein h' is 0 or an integer of 1 to 10, i' is an integer of 1 to 5.

The preferable examples of the fluorine-containing olefin represented bythe formula (1-a) are CH₂ ═CFCF₂ CF₂ CH₂ CH₂ OH, CH₂ ═CFCF₂ CF₂ CF₂ CF₂CH₂ CH₂ OH, CH₂ ═CFCF₂ CF₂ CF₂ CF₂ CF₂ CF₂ CH₂ CH₂ OH, CH₂ ═CFCF₂ CF₂--(CF₂ CF₂)₃ --(CH₂)₃ --CH₂ OH and the like.

The preferable examples of the fluorine-containing olefins representedby the formula (1-b) are ##STR13## and the like.

The preferable examples of the fluorine-containing olefins representedby the formula (1-c) are ##STR14## and the like.

There are various methods of synthesis of the fluorine-containingolefins of the formula (1), and for example, they can be synthesized inthe manner mentioned below.

In the first place, ##STR15## (k' is an integer of 1 to 11).

The fluorine-containing olefin (1-e) can be prepared by telomerizationof tetrafluoroethylene in the presence of a radical initiator after anaddition reaction of iodine with vinylidene fluoride.

The reaction of tetrafluoroethylene with the compound of the formula(1-d) obtained by adding iodine to vinylidene fluoride is carried out inthe presence of a radical initiator such as a peroxide and anazo-compound at a reaction temperature of from room temperature to 200°C., preferably from 40° to 100° C. The tetrafluoroethylene is subjectedto bubbling at normal pressure or under a pressure of not more than 15kgf/cm² G, preferably by keeping at normal pressure or a pressure of notmore than 5 kgf/cm² G. Thus (1-e) can be prepared.

As the peroxides, examples are tert-butyl peroxyisobutyrate, tert-butylperoxy(2-ethylhexanoate), iso-butyrylperoxide, di-iso-propylperoxydicarbonate, di-n-propyl peroxydicarbonate and the like, andexamples of the azo-compounds are azobisisobutyronitrile and the like.No solvent is used, or for example, there can be used Flon type solventssuch as R-113, R-114, R-141b and R-115; chlorine type solvents such ascarbon tetrachloride, chloroform and methylene chloride; hydrocarbontype solvents such as hexane and cyclohexane; aromatic solvents such asbenzene and toluene; and the like. Particularly Flon type solvents arepreferable.

The compounds, i.e. the compound of the formula (1-a) with hydroxylgroup, the compound of the formula (1-b) with glycidyl group and thecompound of the formula (1-c) with glycidyl ether group can besynthesized by using the thus obtained compound of the formula (1-e) asa starting material.

The fluorine-containing olefin of the formula (1-a) with hydroxyl groupcan be synthesized, for instance, in the following manner. ##STR16##That is, ethylene is reacted with the compound of the formula (1-e) inthe presence of a radical initiator to give (1-f), and then water isreacted with the iodine at the ethylene-introduced side to convert to--OH group. After that, the fluorine-containing olefin with hydroxylgroup can be prepared through de-IF reaction by using a metal such asZn.

The compound of the formula (1-f) can be prepared by reacting (1-e) andethylene in the presence of a radical initiator such as a peroxide andan azo-compound or by irradiating ultraviolet rays normally at 20° to200° C., preferably 50° to 100° C. with maintaining a pressure of fromnormal pressure to 50 kgf/cm² G, preferably normal pressure or apressure of not more than 10 kgf/cm² G.

As the above-mentioned peroxides, examples are tert-butylperoxyisobutyrate, tert-butyl peroxy(2-ethylhexanoate),iso-butyrylperoxide, di-iso-propyl peroxydicarbonate, di-n-propylperoxydicarbonate and the like, and examples of the azo-compounds areazobisisobutyronitrile and the like. As the solvent, one similar tothose for the telomerization of tetrafluoroethylene is preferable.

There are various methods adopted for hydroxylation of the iodine atomat the ethylene-introduced side of the ethylene adducts of the formula(1-f). For example, there can be used a method of reacting withchlorosulfonic acid and water in order, a method of reacting with H₂ Oin DMF as described in JP-B-8807/1977, a method of reacting with H₂ O indimethyl sulfoxide as mentioned in JP-B-28585/1990 and the like.

Further the desired fluorine-containing olefin compound (1-h) withhydroxyl group can be prepared through the de-IF reaction from thecompound (1-g) in a polar solvent by using a dehalogenizing agent suchas zinc.

As the solvent in this reaction, there are preferably used, for example,ether type solvents such as monoglyme, diglyme and dioxane; alcohol typesolvents such as methanol and ethanol; ketone type solvents such asacetone and MEK; water; DMF and the like. Particularly methanol, diglymeand the like are preferable.

For the de-IF reaction, usual dehalogenizing agents are used, and inaddition to zinc, there are used magnesium, tin, copper, iron, sodium,manganese and the like. From a point of reaction rate, zinc andmagnesium are preferable. The reaction temperature is from 20° to 150°C., preferably from 40° to 80° C. An amount in molar ratio of thedehalogenizing agent is 1.0 to 5 times, preferably 1.02 to 3 times thatof the compound (1-g). The reaction is preferably carried out by addingzinc powder to the solvent, stirring, dispersing and then heating, andthereafter adding thereto the compound (1-g) slowly and dropwise tocomplete the reaction.

The method of synthesizing a fluorine-containing olefin, i.e. thecompound (1-b) with glycidyl group is, for example, as follows:##STR17## that is, after preparation of the compound (1-i) by reactingallyl alcohol with the compound (1-e) in the presence of a radicalinitiator, dehydroiodination is carried out by using a base to form anepoxy ring. Then the fluorine-containing olefin with glycidyl group canbe prepared by the de-IF reaction by using a metal such as zinc. Thereaction of the compound (1-e) and allyl alcohol can be achieved in thepresence of the radical initiator such as a peroxide or an azo-compoundwhich is similar to one used in the reaction with tetrafluoroethylene orethylene, at a reaction temperature of 20° to 200° C., preferably 50° to150° C.

Subsequently the compound (1-j) with epoxy ring can be prepared byreacting the compound (1-i) and a little bit excess amount of the basefor the de-HI reaction. As the base, preferable are a hydroxide such assodium hydroxide, potassium hydroxide or calcium hydroxide, an alkallinemetal carbonate such as sodium carbonate or sodium hydrogencarbonate, ametal alkoxide such as sodium methoxide, sodium ethoxide orpotassium-tert-butoxide, a tertiary amine such as triethylamine orpyridine, and the like. Also in order to prevent the formed epoxy ringfrom opening, particularly preferable are sodium hydroxide, potassiumhydroxide, calcium hydroxide, alkalline metal carbonates and tertiaryamines.

The reaction proceeds without a solvent. In case where a solvent isused, there are preferably used, for example, water, an alcohol typesolvent such as methanol or ethanol, an ether type solvent such astetrahydrofuran, dioxane, monoglyme or diglyme, a ketone type solventsuch as acetone, methyl ethyl ketone or methyl isobutyl ketone, atertiary amine type solvent such as triethylamine or pyridine,dimethylformamide, dimethylsulfoxide, and the like. Also in order toprevent the formed epoxy ring from opening, it is preferable that nosolvent is used or even if the solvent is used, particularly preferableare ether type, ketone type and tertiary amine type solvents,dimethylformamide, dimethylsulfoxide and the like.

The de-IF reaction from the obtained compound (1-j) can be carried outby using a metal such as Zn in the same manner as in the reaction forthe de-IF reaction of the compound (1-g). As the solvent, the use ofwater and the alcohol type solvent such as methanol or ethanol should beavoided in order to prevent the formed epoxy ring from opening.

There are various methods to synthesize the fluorine-containing olefin(1-c) with glycidyl ether group. The olefin can be prepared by reactinga fluorine-containing olefin (1-h) with hydroxyl group andepichlorohydrine. ##STR18##

For example, acidic catalysts of Lewis acid such as BF₃ (C₂ H₅ OC₂ H₅)₃and SnCλ₄ can be used, and BF₃ (C₂ H₅ OC₂ H₅)₃ is preferable. Thecompound (1-m) can be prepared by acting the acidic catalyst on thecompound (1-h) and epichlorohydrine to form the compound (1-l) and thencarrying out dehydrochlorination reaction by using a base.

The reaction temperature is from -10° to 200° C., preferably from 0° to100° C. A solvent may not be used, but, for example, an ether typesolvent such as monoglyme, diglyme, dioxane or tetrahydrofuran, a ketonetype solvent such as acetone or MEK, a hydrocarbon type solvent such ashexane or cyclohexane, a chlorine type solvent such as chloroform,dichloromethane or carbon tetrachloride, and a Flon type solvent such asR-113, 141b or 115 are preferable, and the ether type solvent isparticularly preferable.

The dehydrochlorination reaction of the compound (1-l) can be carriedout in the same manner as in the above-mentioned preparation of thecompound (1-j) through the de-HI reaction of the compound (1-i) by usinga base.

Also through the reaction of a base, an equivalent or more amount ofepichlorohydrine and the compound (1-h), the compound (1-m) can besynthesized. As the base, there are preferably used sodium hydroxide,potassium hydroxide, sodium hydride and the like. The reactiontemperature is from 20° to 200° C., preferably from 50° to 150° C. Asolvent may not be used, but, for example, when used, preferable are anether type solvent such as monoglyme, diglyme, dioxane ortetrahydrofuran, a ketone type solvent such as acetone or MEK, ahydrocarbon type solvent such as hexane or cyclohexane, a chlorine typesolvent such as chloroform, dichloromethane or carbon tetrachloride, aFlon type solvent such as R-113, 141 b, 115 or the like. No solvent orthe use of ether type solvent is particularly preferable.

Another structure of R_(f) ⁶ in the fluorine-containing olefin of theformula (IV) is an ether group represented by --OR_(f) ⁷ --, and --R_(f)⁷ -- is a fluorine-substituted alkylene group having 1 to 40 carbonatoms or a fluorine-substituted ether group having 3 to 50 carbon atomsand includes linear or branched groups or a mixture thereof.

Among them, preferable typical example is a fluorine-containing olefinrepresented by the formula (2): ##STR19## wherein X⁴ is ##STR20## A⁵ is##STR21## B⁵ is CF₃ or F, j' is 0 or an integer of 1 to 5, 1' is 0 or aninteger of 1 to 10.

Further preferable typical examples are fluorine-containing olefinsrepresented by the compounds (2-a), (2-b), (2-c) and (2-d): ##STR22##wherein m' is 0 or an integer of 1 to 5, n' is 0 or an integer of 1 to10, ##STR23## wherein o' is 0 or an integer of 1 to 5, p' is 0 or aninteger of 1 to 10, ##STR24## wherein q' is 0 or an integer of 1 to 5,r' is 0 or an integer of 1 to 10 and ##STR25## wherein s' is 0 or aninteger of 1 to 5, t' is 0 or an integer of 1 to 10.

The preferable examples of the fluorine-containing olefins representedby the formula (2-a) are ##STR26## and the like.

The preferable examples of the fluorine-containing olefins representedby the formula (2-b) are ##STR27## and the like.

The preferable examples of the fluorine-containing olefins representedby the formula (2-c) are ##STR28## and the like.

The preferable examples of the fluorine-containing olefins representedby the formula (2-d) are ##STR29## and the like.

The fluorine-containing olefin of the formula (2) can be derived from acorresponding acid fluoride prepared through the methods described inJP-A-137928/1985 and JP-A-12734/1987 or from a correspondingcarboxylester prepared through the reaction of the above-mentioned acidfluoride and a lower alcohol. For example, the fluorine-containingolefin with hydroxyl group represented by the formula (2-a) can besynthesized by carrying out a reduction reaction, by using a reducingagent, of a methyl ester group in the fluorine-containing ether compoundrepresented by the formula (2-e): ##STR30## wherein X⁵ is Br or I, u' is0 or an integer of 1 to 5, v' is 0 or an integer of 1 to 10, and then ade-X⁵ F reaction (X⁵ is Br or I) by using a metal such as zinc, or bycarrying out previously the de-X⁵ F reaction to form a double bond andthen acting thereto a reducing agent.

In the reduction reaction of the compound of the formula (2-e), therecan be used usual reducing agents, for example, hydrogen (platinumoxide, palladium catalyst and the like are used), lithium aluminumhydride, boron hydride, sodium boron hydride, lithium boron hydride andthe like, and sodium boron hydride is most preferable. The molar ratioof boron hydride to ester is from about 0. 3 to about 1.2, preferablyfrom about 0.4 to about 0.8. As the solvent, preferable are water, analcohol type solvent such as methanol or ethanol, an ether type solventsuch as ether, tetrahydrofuran, monoglyme, diglyme or dioxane, and ahydrocarbon type solvent such as pentane, hexane or cyclohexane. Amongthem, the alcohol type solvent is preferable, and ethanol is mostpreferable.

The reaction temperature is from -20° to 80° C. preferably from -10° to20° C., and it is particularly preferable to carry out the reaction inthe range of -5° to 10° C. from a point of decreasing by-products due tothe hydrogenation of X⁵ --CH₂ -- (X⁵ is Br or I) by a reducing agent andthe reaction with CH₂ ═CF-- bond. The reaction for forming a double bondthrough the de-X⁵ F reaction (X⁵ is Br or I) from X⁵ CH₂ CF₂ -- can beachieved in the same manner as in the above-mentioned reaction with Zn.

The fluorine-containing olefin with glycidyl group represented by theformula (2-c) can be synthesized through the reaction ofepichlorohydrine and the corresponding fluorine-containing olefin withhydroxyl group of the formula (2-a). The synthesis is carried out in thesame manner as in the above-mentioned preparation of thefluorine-containing olefin with glycidyl group of the formula (1-m) fromthe compound of the formula (1-h).

The fluorine-containing olefin with hydroxyl group represented by theformula (2-b) can also be derived from the corresponding carboxylesterin the same manner.

That is, the compound (2-b) can be synthesized in the same manner as insynthesis of the fluorine-containing olefin of the formula (2-a) fromthe compound of the formula (2-e) except that the formula (2-f) is used.##STR31## wherein X⁶ is Br or I, w' is 0 or an integer of 1 to 5, x' is0 or an integer of 1 to 10.

Also the fluorine-containing olefin with glycidyl group represented bythe formula (2-d) can also be synthesized through the reaction of thecompound (2-b) and epichlorohydrine in the same manner as in thepreparation of the compound (2-c).

The second fluorine-containing olefin with functional group of thepresent invention is a fluorine-containing olefin having carboxylic acidor a derivative thereof as a functional group and being represented bythe formula (V)

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.8 --(CH.sub.2).sub.m --COOR.sup.4 (V)

wherein R⁴ is H, an alkyl group having 1 to 6 carbon atoms, Na, K, Li orNH₄, R_(f) ⁸ is a fluorine-substituted alkylene group having 3 to 40carbon atoms or --OR_(f) ⁹ --(R_(f) ⁹ is a fluorine-substituted alkylenegroup having 2 to 40 carbon atoms or a fluorine-substituted ether grouphaving 3 to 50 carbon atoms), m is 0 or an integer of 1 to 6.

One of the structures of Rf⁸ in the fluorine-containing olefins of theformula (V) is a fluorine-substituted alkylene group having 3 to 40carbon atoms, which includes linear form, branched form or mixed formthereof.

Among them, preferable typical examples are fluorine-containing olefinsrepresented by the formula (3):

    CH.sub.2 ═CFCF.sub.2 CF.sub.2 --(CF.sub.2 CF.sub.2).sub.y' --(CH.sub.2).sub.z' --COOR.sup.5                          (3)

wherein R⁵ and z' are the same as R⁴ and m of the above-mentionedformula (V), respectively, y' is an integer of 1 to 10.

The preferable examples of the fluorine-containing olefins representedby the formula (3) are CH₂ ═CFCF₂ CF₂ CF₂ CF₂ COOH, CH₂ ═CFCF₂ CF₂ (CF₂CF₂)₂ --COOH, CH₂ ═CFCF₂ CF₂ (CF₂ CF₂)₃ --COOH, CH₂ ═CFCF₂ CF₂ CF₂ CF₂CH₂ COOH, CH₂ ═CFCF₂ CF₂ CF₂ CF₂ COOCH₃, CH₂ ═CFCF₂ CF₂ (CF₂ CF₂)₂--COOCH₃, CH₂ ═CFCF₂ CF₂ CF₂ CF₂ COONa, CH₂ ═CFCF₂ CF₂ (CF₂ CF₂)₂--COONa, CH₂ ═CFCF₂ CF₂ CF₂ CF₂ COONH₄, CH₂ ═CFCF₂ CF₂ (CF₂ CF₂)₂--COONH₄, and the like.

In case of the fluorine-containing olefin represented by the formula(3), for example, the fluorine-containing olefin with carboxyl group inwhich R is H, various synthesis methods can be employed. One of themethods is, for example, such that polyfluoroalkyliodide of theabove-mentioned (1-e) and carbon dioxide gas are reacted in the presenceof zinc powder in an amount of 2 equivalents or more to the raw material(1-e) for acid hydrolysis to give the fluorine-containing olefin.##STR32## (k' is an integer of 2 or more)

The carbon dioxide gas can be supplied by bubbling at normal temperatureor in an autoclave under pressure. As the solvents, preferable aredimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and the like. Dimethylformamide and dimethylacetamide areparticularly preferable. The reaction pressure is in the range of 0 to50 kgf/cm² G, preferably 0 to 20 kgf/cm² G.

The reaction temperature is from 0° to 150° C., preferably from 10° to80° C.

Another method to synthesize the fluorine-containing olefin is a methodin which oxidation of hydroxyl group of the compound of theabove-mentioned formula (1-g) is carried out by using a usual oxidizingagent, followed by de-IF reaction by using Zn or the like. ##STR33## (k'is an integer of 2 or more)

As the oxidizing agents, there can be preferably used various ones, forexample, a chromium type oxidizing agent such as a dichromate-sulfuricacid mixture or a chromium trioxide-pyridine mixture, a manganese typeoxidizing agent such as manganese dioxide or potassium permanganate,silver oxide, nitric acid, an organic peroxide and the like, andparticularly the dichromate-sulfuric acid mixture is preferable. Thereaction temperature varies with the oxidizing agent to be used, and isusually from -20° to 150° C., preferably from -10° to 100° C., morepreferably from -5° to 50° C. The fluorine-containing olefin (3-c) withcarboxyl group can be prepared by using the obtained (3-b) and zinc inthe same manner as mentioned above.

Another structure of R_(f) ⁸ in the fluorine-containing olefin of theformula (V) is an ether group represented by --OR_(f) ⁹, and R_(f) ⁹ isa fluorine-substituted alkylene group having 2 to 40 carbon atoms or afluorine-containing ether group having 3 to 50 carbon atoms, and may bein the linear, branched or a mixture form.

Among them, the preferable typical examples are the fluorine-containingolefins represented by the formula (4): ##STR34## wherein R⁶ is the sameas R⁴ of the formula (V), A⁶ is ##STR35## B⁶ is CF₃ or F, a" is 0 or aninteger of 1 to 5, b" is 0 or an integer of 1 to 10, B⁶ is CF₃ in caseof a"=b"=0.

Among the preferable examples of the formula (4), thefluorine-containing olefins with carboxyl group are ##STR36## and thelike.

The above-mentioned carboxylic acid derivative is an alkyl ester, sodiumsalt, potassium salt, lithium salt or ammonium salt of theabove-mentioned carboxylic acids, and the preferable examples thereofare ##STR37## and the like.

There are various methods of synthesis of the carboxylic acidrepresented by the formula (4) and the derivative thereof, and they canbe synthesized by using the above-mentioned formula (2-e) or (2-f) as astarting material. ##STR38##

For example, the fluorine-containing olefin (4-a) with ester group canbe prepared through the de-X⁵ F reaction (X⁵ : I or Br) by using zinc inthe same manner as mentioned above in case where the compound (2-e) isused.

The fluorine-containing olefin with carboxyl group can be prepared bythe hydrolysis of the ester group of the compound (4-a) obtained throughthe above-mentioned de-X⁵ F reaction (X⁵ : I, Br). ##STR39##

That is, the fluorine-containing olefin with carboxyl group can beprepared by reacting the fluorine-containing olefin (4-a) with an alkalihydroxide (MOH) such as sodium hydroxide to obtain the compound (4-b),and then applying thereto an inorganic protonic acid such ashydrochloric acid or sulfuric acid.

In the above-mentioned hydrolysis, there can be applied an inorganicprotonic acid such as hydrochloric acid, sulfuric acid or nitric acid inaddition to an alkali hydroxide such as sodium hydroxide, potassiumhydroxide or lithium hydroxide.

In case of the alkali hydrolysis, the alkali hydroxide is used in alittle excess equivalents, i.e. 1.0 to 1. 1 equivalent to the compound(4-a). As the solvent, water or an alcohol can be used, and methanol orethanol is preferable. The reaction temperature is preferably from 50 to150° C., more preferably from 10° to 50° C.

The fluorine-containing olefin (4-c) with carboxyl group can be obtainedby adding an inorganic protonic acid (hydrochloric acid or sulfuric acidis preferable) to the solution of the obtained compound (4-b) until thesolution becomes acid at pH of 2 or lower.

The sodium salt, potassium salt, lithium salt or ammonium salt of thecarboxylic acid can be obtained by a usual method in which the obtainedfluorine-containing olefin (4-c) with carboxyl group is neutralized byusing an aqueous solution of sodium hydroxide, potassium hydroxide,lithium hydroxide or ammonia, respectively.

The corresponding fluorine-containing olefin (4-d) with carboxylestergroup, fluorine-containing olefin (4-f) with carboxyl group and theiralkali metal salt or ammonium salt can be prepared similarly in themanner as mentioned below also in case where the formula (2-f) is usedas a starting material. ##STR40##

The fluorine-containing olefin of the present invention is a usefulcompound which can introduce a reactive group such as hydroxyl group,carboxyl group and glycidyl group to a side chain of afluorine-containing copolymer, and has the following characteristics:

(1) The polymerization rate is not decreased remarkably and excellentcopolymerizability is assured at the time of copolymerization withvarious ethylenically unsaturated compounds, particularly ethylenicallyunsaturated fluorine-containing compound such as tetrafluoroethylene andvinylidene fluoride,

(2) Thermal stability and chemical stability of the resultingfluorine-containing copolymer are not lowered,

(3) The fluorine-containing olefin itself is stable under the alkalinecondition, is not affected by the conditions in use and is easy to behandled, and

(4) The process for synthesizing the fluorine-containing olefin isrelatively easy and economical, and is industrially produceable.

Also there is a possibility that the fluorine-containing olefin itselfis used as a macromer. The fluorine-containing compound having thestructure such as carboxyl group, an alkali metal salt thereof orammonium salt thereof generally has a high surface activity and isuseful as an emulsifying agent. The fluorine-containing olefin withcarboxyl group of the present invention, its Na, K, Li or ammonium saltis represented by the formula (5):

    CH.sub.2 ═CFCF.sub.2 R.sub.f.sup.10 --(CH.sub.2).sub.d "--COOR.sup.7 (5)

wherein R⁷ is selected from H, Na, K and NH₄, d" is the same as m of theformula (V);

and R_(f) ¹⁰ in the structure is a fluorine-containing olefin of a longchain which comprises a fluorine-containing alkylene group having 3 to40 carbon atoms or --OR_(f) ¹¹ --(R_(f) ¹¹ is a fluorine-containingalkylene group having 2 to 50 carbon atoms or a fluorine-containingether group having 3 to 50 carbon atoms). Namely, R_(f) ¹⁰ has 3 or moreof carbon atoms, or in case that R_(f) ¹⁰ contains an ether bond, thesum of carbon atoms and oxygen atoms relating to the ether bond is 3 ormore. As compared with a fluorine-containing olefin in which the numberof carbon atoms of R_(f) ¹⁰ or the sum of carbon atoms and oxygen atomsrelating to the ether bond of R_(f) ¹⁰ is 1 or 2, the above-mentionedlong-chain fluorine-containing olefin has a high surface activity and isusable as a reactive emulsifying agent.

The use of the olefin, for example, in emulsion polymerization,contributes to making the emulsion particle size fine, increasing ayield and a reaction rate, and also making it possible to achievesoap-free polymerization.

Also, high contribution to dispersing stability of the emulsion obtainedby emulsion polymerization is assured and it is possible to use no usualfree emulsifying agent or decrease an amount thereof. Therefore it canbe expected that the emulsion itself is used as a stable aqueousemulsion paint having a high weather resistance and high chemicalresistance.

The second one of the present inventions relates to afluorine-containing polymer with functional group, which is prepared bycopolymerizing a fluorine-containing olefin (A) with any of hydroxylgroup, glycidyl group, carboxyl group or carboxylester group and anethylenically unsaturated compound (B).

As the prior arts relating to a fluorine-containing polymer withfunctional group, various copolymers of a fluorine-containingethylenically unsaturated compound copolymerized with a hydrocarbon typemonomer with functional group are reported.

For example, there are reported a copolymer of a hydroxyalkyl vinylether and tetrafluoroethylene (U.S. Pat. No. 3,306,879), a copolymerprepared by using glycidyl vinyl ether (JP-B-52645/1984) and a copolymerprepared by using a vinyl ether compound with carboxyl group(JP-A-110646/1989). With respect to these fluorine-containing polymersprepared by using such hydrocarbon type monomers with functional group,thermal resistance at both of their side chain and trunk chain portionsis insufficient, and decomposition occurs on a part thereof particularlywhen melting and kneading with a heat-resisting thermoplastic resin at ahigh temperature. Thus desired external appearance and physicalproperties cannot be obtained.

On the other hand, as a fluorine-containing polymer prepared by using afluorine containing olefin with functional group, there are known thefluorine-containing polymers (JP-A-143888/1975) prepared by using##STR41## wherein R is H or methyl, X' is F or Cλ, and hemi-acetal.Those polymers, however, have tertiary hydrogen like ##STR42## in thetrunk chain, and thus there are drawbacks such that thermal resistanceof the obtained copolymer is decreased to easily cause coloring anddeterioration at a high temperature.

Also as a fluorine-containing polymer prepared by copolymerizing amonomer having a perfluorovinyl group, there are reported afluorine-containing polymer prepared by using a fluorine-containingmonomer represented by CF₂ ═CF(CF₂).sub.α --(CH₂).sub.β --X, wherein Xis OH, ##STR43## or --COOH (JP-A-675 17/1985), and fluorine-containingpolymers prepared by copolymerizing the respective fluorine-containingmonomers of CF₂ ═CFO--R_(f') --COOH (JP-A-234753/1991) and CF₂═CFOR_(f") --CH₂ OH (JP-A-91513/1991, JP-A-503935/1993). The reactivityof polymerization of these monomers having the perfluorovinyl group withethylene, tetrafluoroethylene, chlorotrifluoroethylene and the like islow, and in order to obtain a polymer having a desired composition, alarge amount of monomers is required. Also a rate of copolymerizationdecreases remarkably.

Further these monomers require complicated synthesizing process stepsand are expensive, and thus are industrially less practical.

Also there is a report such that a fluorine-containing polymer withfunctional group is prepared by dehydrofluorination of a vinylidenefluoride type polymer and addition of a nucleophilic functional group tothe formed double bond (Polym Mater. Sci Eng., 49,518 (1983),JP-A-112616/1993). The fluorine-containing polymers obtained through theabove-mentioned polymer reaction have such problems that the functionalgroups are difficult to be uniformly introduced thereto and an irregulardistribution of composition occurs, and that the side chain portion ofthe prepared polymer is insufficient in thermal resistance and chemicalresistance due to the addition of the nucleophilic reactive reagent, andthat the polymers are limited to only the vinylidene fluoride typepolymers.

An object of the present invention is to solve the above-mentionedproblems and to provide a novel fluorine-containing polymer in which auseful functional group such as hydroxyl group, glycidyl group orcarboxyl group is introduced without impairing excellent thermalresistance, chemical resistance and the like which thefluorine-containing resin possesses.

The present invention particularly relates to a fluorine-containingpolymer with functional group, which is characterized in that thepolymer itself has enough thermal resistance to melting and kneading ata high temperature when blended with a heat-resisting thermoplasticresin, and further in that a homogeneous dispersion can be formed sincethe fluorine-containing polymer and the thermoplastic resin have a goodaffinity with each other in the obtained blend.

The present invention relates to a novel fluorine-containing polymerwith functional group which is a copolymer comprising 0.01 to 80% bymole of (A) and 20 to 99.99% by mole of (B) and having a number averagemolecular weight of 2,000 to 20,000,000.

The compound (A) comprises one or more monomers represented by theformula (I):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.1 --(CH.sub.2).sub.α --X.sup.1 (I)

wherein X¹ is --CH₂ OH, --COOR¹ (R¹ is H, an alkyl group having 1 to 6carbon atoms, Na, K, Li or NH₄), ##STR44## R_(f) ¹ is afluorine-substituted alkylene group having 1 to 40 carbon atoms or--OR_(f) ² (R_(f) ² is a fluorine-substituted alkylene group having 1 to40 carbon atoms or a fluorine-substituted ether group having 3 to 50carbon atoms), a is 0 or an integer of 1 to 6, and the compound (B)comprises one or more monomers selected from the group consisting of themonomers represented by the formula (II): ##STR45## wherein Y¹ is F, Cλ,H or CF₃, Y² is F, Cλ, H, R_(f) ³ (R_(f) ³ is a perfluoroalkyl grouphaving 1 to 10 carbon atoms) or ##STR46## (R_(f) ⁴ is a perfluoroalkylgroup having 1 to 6 carbon atoms, b is 0 or an integer of 1 to 5) andthe formula (III): ##STR47## wherein Z¹ is F, H, an alkyl group having 1to 6 carbon atoms or a perfluoroalkyl group having 1 to 10 carbon atoms,Z² is H, Cλ, an alkyl group having 1 to 6 carbon atoms or --(CF₂)_(d)--Z³ (d is an integer of 1 to 10, Z³ is F or H).

That is, the polymer of the present invention is a novelfluorine-containing polymer with functional group, which is prepared bycopolymerizing 0.01 to 80% by mole of a fluorine-containing olefin (A)of the specific structure represented by the formula (I) having anyfunctional group of hydroxyl group, carboxyl group, carboxylic acidderivative, glycidyl group or glycidyl ether group with theethylenically unsaturated compound (B).

In the fluorine-containing polymer of the present invention, thefluorine-containing olefin (A) with functional group is one representedby the formula (I), and the polymer prepared by copolymerizing theolefin having X¹, as a functional group, such as --CH₂ OH, --COOH,##STR48## is preferable. In the compound (A), R_(f) ¹ is thefluorine-containing alkylene group or the fluorine-containingoxyalkylene group represented by --OR_(f) ², and R_(f) ² is thefluorine-containing alkylene group or the fluorine-containing ethergroup. Particularly in case where importance is attached to thermalresistance, it is preferable that R_(f) ¹ is more highlyfluorine-substituted, and a perfluorinated alkylene group or oxyalkylenegroup is preferable. Also, with respect to a carbon chain length ofR_(f) ¹, about 1 to about 40 carbon atoms can be used depending on uses,and it is preferable that R_(f) ¹ has about 2 to about 20 carbon atomsfrom the viewpoints of reactivity of polymerization and physicalproperties of the copolymer.

The preferable examples of R_(f) ¹ are ##STR49## (e is 0 or an integerof 1 to 10), ##STR50## (g is 0 or an integer of 1 to 5, h is 0 or aninteger of 1 to 10) and the like.

Further as the examples of the compound (A) in which X¹ is --CH₂ OH,preferable are ##STR51## and the like, and particularly preferable are##STR52##

As the compounds in which X¹ is --COOH group, preferable are ##STR53##and the like, and particularly preferable are ##STR54##

As the compounds in which X¹ is a carboxylic acid derivative, preferableare ##STR55## and the like.

As the compounds in which X¹ is ##STR56## preferable are ##STR57## andthe like, and particularly preferable are ##STR58##

Another copolymerizing component (B) of the polymer of the presentinvention comprises one or more monomers selected from the groupconsisting of the monomers represented by the formula (II): ##STR59##wherein Y¹ is F, Cλ, H or CF₃, Y² is F, Cλ, H, R_(f) ³ (R_(f) ³ is aperfluoroalkyl group having 1 to 10 carbon atoms) or ##STR60## (R_(f) ⁴is a perfluoroalkyl group having 1 to 6 carbon atoms, b is 0 or aninteger of 1 to 5) and the formula (III): ##STR61## wherein Z¹ is F, H,an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl grouphaving 1 to 10 carbon atoms, Z² is H, Cλ, an alkyl group having 1 to 6carbon atoms or --(CF₂)_(d) --Z³ (d is an integer of 1 to 10, Z³ is F orH).

As the examples of the monomers represented by the formula (II),preferable are

CF₂ ═CF₂, CF₂ ═CFCl, CF₂ ═CFCF₃, CF₂ ═CH₂, CF₂ ═C(CF₃)₂, CF₂ --CFOCF₃,CF₂ ═CFOC₃ F₇, ##STR62## and the like.

As the examples of the monomers represented by the formula (III),preferable are

CH₂ ═CHF, CH₂ ═CFCF₃, CH₂ ═CHCF₃, CH₂ ═C(CF₃)₂, CH₂ ═CH₂, CH₂ ═CHCH₃,CH₂ ═CHC₂ H₅, CH₂ ═C(CH₃)₂, CH₂ ═CHCl, CH₂ ═CHC₄ F₉, CH₂ ═CF(CF₂)₃ --Hand the like.

The molar ratio of the fluorine-containing olefin (A) with functionalgroup to the other monomer (B) in the fluorine-containing polymer of thepresent invention may vary depending on use and kind of copolyemrs, andis usually (A)/(B)=0.01 to 80/99.99 to 20% by mole. Particularly theproportion of (A)/(B)=0.01 to 30/99.99 to 70% by mole is preferable inorder to obtain a composition having an excellent dispersibility whenmixing with the heat-resisting thermoplastic resin.

Further in the fluorine-containing polymer of the present invention, inaddition to the above-mentioned compounds (A) and (B), an ethylenicallyunsaturated compound (C) which is copolymerizable with the compounds (A)and (B) may be copolymerized.

As the above-mentioned ethylenically unsaturated compounds, there arealkyl vinyl ethers or vinyl esters represented by the formula:

    CH.sub.2 ═CH--O--(C═O).sub.e" R.sup.8

wherein R⁸ is an aliphatic group having 1 to 17 carbon atoms, analicyclic group having 3 to 17 carbon atoms or a fluoroalkyl grouphaving 1 to 20 carbon atoms, e" is 0 or 1, and examples thereof are, forinstance, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether,isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether,cyclohexyl vinyl ether, 2,2,2-trifluoroethyl vinyl ether,2,2,3,3-tetrafluoropropyl vinyl ether, 2,2,3,3,3-pentafluoropropyl vinylether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate,vinyl versatate, vinyl cyclohexanedicarboxylate and the like.

Further there are compounds represented by the formula: ##STR63##wherein Z⁵ is H, Cλ, F, CH₃ or CF₃, R⁹ is H, Cλ, F, an aliphatic grouphaving 1 to 17 carbon atoms, an alicyclic group having 3 to 17 carbonatoms or a fluoroalkyl group having 1 to 20 carbon atoms. As theexamples thereof, there are, for instance, isobutyl acrylate, methylacrylate, ethyl methacrylate, 2,2,3,3,3-pentafluoropropylα-fluoroacrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoropentylα-trifluoromethylacrylate, cyclohexyl acrylate,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15,15-nonacosafluoropentadecyl acrylate,octyl α-chloroacrylate, octadecyl acrylate and the like.

Also, the compounds represented by the formula:

    CH.sub.2 ═CHCH.sub.2 Z.sup.6

wherein Z⁶ is chlorine atom or an alkoxyl group having 1 to 8 carbonatoms can be used, and the examples thereof are, for instance, allylchloride, allyl methyl ether, allyl isopropyl ether, allyl octyl etherand the like.

In addition, there are styrene, styrene derivatives, dialkyl esters ofmaleic acid and the like.

In case where the ethylenically unsaturated compound (C) iscopolymerized, the molar ratio of each monomer in the polymer variesdepending on use and kind of the copolymers, and (A)/((B)+(C)) isusually 0.01 to 80/99.99 to 20% by mole. With respect to (B) and (C), itis preferable that (C) is not more than 60% by mole per the sum of (B)and (C). Particularly in case of the fluorine-containing polymer to beused when mixing with a heat-resisting thermoplastic resin, since theportion from the compound (C) may be most thermally instable, it ispreferable that (A), (B) and (C) are 0.01 to 30% by mole, 70 to 99.99%by mole and not more than 20% by mole, respectively to the total molesof all monomers.

In the fluorine-containing polymers of the present invention, theperformances, physical properties and uses complying therewith dependlargely on the kind and proportion (ratio) of the compound (B).

As the preferable structure of the fluorine-containing polymer of thepresent invention, the compound (B) is roughly classified into twogroups. One group mainly comprises tetrafluoroethylene orchlorotrifluoroethylene, and another group mainly comprises vinylidenefluoride. That is, the first group is a fluorine-containing polymerwhich is prepared by copolymerizing a fluorine-containing olefin (A)with functional group and the compound (B) which essentially containstetrafluoroethylene or chlorotrifluoroethylene, and, if necessary, othercopolymerizable monomers. The fluorine-containing polymer comprises 0.01to 30% by mole of (A) on the basis of the total moles of all monomersand not less than 30% by mole of tetrafluoroethylene orchlorotrifluoroethylene per the total moles of the monomers exceptingthe fluorine-containing olefin (A).

As the other copolymerizable monomers in the above-mentioned polymer,preferable are vinylidene fluoride, hexafluoropropene,hexafluoroisobutene, a perfluoro vinyl ether represented by the formula:##STR64## wherein R_(f) ⁵ is a perfluoroalkyl having 1 to 6 carbonatoms, j is 0 or an integer of 1 to 5, a fluorine-containing olefinrepresented by the formula: ##STR65## wherein Z³ is H or F, Z⁴ is H orF, i is an integer of 1 to 10, and ethylene, propylene, 1-butene,isobutene and the like.

As the specific examples of the fluorine-containing polymer of thepresent invention which mainly comprises tetrafluoroethylene orchlorotrifluoroethylene, there are preferably, for instance, a copolymerof the fluorine-containing olefin (A) and tetrafluoroethylene (so-calledPTFE with functional group); a copolymer of the compound (A),tetrafluoroethylene and hexafluoropropene (FEP with functional group); acopolymer of the compound (A), tetrafluoroethylene and theabove-mentioned perfluoro(vinyl ether) in an amount of not more than 10%by mole per all monomers excepting (A) (PFA with functional group); acopolymer of the compound (A), tetrafluoroethylene orchlorotrifluoroethylene, ethylene and further a copolymerizablefluorine-containing olefin as a third monomer if necessary (E(C)TFE withfunctional group); an elastomeric copolymer of the compound (A),tetrafluoroethylene and propylene; an elastomeric copolymer of thecompound (A), tetrafluoroethylene and a perfluoro (vinyl ether) in anamount of not less than 15% by mole per all the monomers excepting (A);and the like.

Particularly when the fluorine-containing polymer is blended with aheat-resisting thermoplastic resin, though it varies depending on kindof the heat-resisting thermoplastic resin, a processing temperaturerelatively equivalent to that of the heat-resisting thermoplastic resincan be selected in melt-blending and molding, and a fluorine-containingpolymer of which thermal stability is maintained at the processingtemperature is preferable. Among the above-mentioned examples,particularly preferable are the PFA type copolymer comprising thecompound (A), and also the E(C)TFE type copolymer and the elastomericcopolymer containing the compound (A) and mainly comprisingtetrafluoroethylene.

Among them, the PFA type copolymer is one particularly comprising 0.01to 30% by mole of the fluorine-containing olefin (A) with functionalgroup per the total moles of all monomers, 95 to 99.7% by mole oftetrafluoroethylene per the total moles of the monomers excepting thecompound (A) and 0.3 to 5.0% by mole of a perfluoro(vinyl ether)represented by the formula:

    CF.sub.2 ═CFOR.sub.f.sup.12

wherein R_(f) ¹² is a perfluoroalkyl group having 1 to 6 carbon atomsper the total moles of the monomers excepting the compound (A).

Also the E(C)TFE type copolymer is particularly one comprising 0.01 to30% by mole of the fluorine-containing olefin (A) with functional groupper the total moles of all the monomers, 30 to 70% by mole oftetrafluoroethylene per the total moles of the monomers excepting thecompound (A), 30 to 70% by mole of ethylene and 0 to 15% by mole of thefluorine-containing olefin as a third component if necessary. As thefluorine-containing olefin as the third component, there can be used afluorine-containing olefin represented by ##STR66## wherein Z³ is H orF, Z⁴ is H or F, i is an integer of 1 to 10, perfluoro(vinyl ether),hexafluoropropylene, hexafluoroisobutylene and the like, and ##STR67##(Z³, Z⁴ and i are the same as above) and hexafluoroisobutylene areparticularly preferable.

On the other hand, as the elastomeric copolymer with functional groupand mainly comprising tetrafluoroethylene, there is one comprising 0.01to 30% by mole of the fluorine-containing olefin (A) with functionalgroup per the total moles of all monomers and 40 to 70% by mole oftetrafluoroethylene and 30 to 60% by mole of propylene per the totalmoles of the monomers excepting the compound (A). Also it is possiblethat additionally the copolymerizable components such as vinylidenefluoride, hexafluoropropylene, chlorotrifluoroethylene andperfluoro(vinyl ether) may be contained in an amount of not more than20% by mole per the total moles of the monomers excepting the compound(A).

Another elastomeric polymer is a polymer of tetrafluoroethylene andperfluoro(vinyl ether), and comprises 0.01 to 30% by mole of thecompound (A) per the total moles of all monomers and 40 to 85% by moleof tetrafluoroethylene on the basis of all the monomers excepting thecompound (A) and 15 to 60% by mole of a perfluoro(vinyl ether)represented by the formula: ##STR68## wherein R_(f) ⁵ is aperfluoroalkyl group having 1 to 6 carbon atoms, j is 0 or an integer of1 to 5.

The second group of the preferable fluorine-containing polymer of thepresent invention is a polymer mainly comprising vinylidene fluoride.

That is, the polymer is a copolymer prepared by copolymerizing thefluorine-containing olefin (A) with functional group and the compound(B) containing essentially vinylidene fluoride, and, if necessary, othermonomers. This fluorine-containing polymer comprises 0.01 to 30% by moleof the compound (A) per the total moles of all monomers and not lessthan 40% by mole of vinylidene fluoride per the total moles of themonomers excepting the compound (A).

As the other copolymerizable monomers in the above-mentioned polymer,the preferable examples are tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropene, hexafluoroisobutene,perfluoro(vinyl ether) and the like.

As the preferable examples of the fluorine-containing polymer of thepresent invention, which mainly comprises vinylidene fluoride, there area copolymer of the fluorine-containing olefin (A) with functional groupand vinylidene fluoride (so-called PVdF with functional group), acopolymer of the compound (A), vinylidene fluoride andtetrafluoroethylene, a copolymer of the compound (A), vinylidenefluoride and hexafluoropropylene, a copolymer of the compound (A),vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, acopolymer of the compound (A), vinylidene fluoride, tetrafluoroethyleneand chlorotrifluoroethylene, and the like.

Further these fluorine-containing polymers mainly comprising vinylidenefluoride can be made resinous or elastomeric polymers by the presence orabsence of other copolymerizable monomer component and by selecting kindand proportion thereof.

Among them, particularly preferable examples of resinous polymers forblending with a heat-resisting thermoplastic resin are a copolymercomprising 0.01 to 30% by mole of the fluorine-containing olefin (A)with functional group and 70 to 99.9% by mole of vinylidene fluoride, acopolymer comprising 0.01 to 30% by mole of the compound (A) per thetotal moles of all monomers, and, per the total moles of the monomersexcepting the compound (A), 70 to 99% by mole of vinylidene fluoride and1 to 30% by mole of tetrafluoroethylene, a copolymer comprising 0.01 to30% by mole of the compound (A) per the total moles of all monomers and,per the total moles of the monomers excepting the compound (A), 50 to99% by mole of vinylidene fluoride, 0 to 30% by mole oftetrafluoroethylene and 1 to 20% by mole of chlorotrifluoroethylene, acopolymer comprising 0.01 to 30% by mole of the compound (A) on thebasis of all monomers and, per the total moles of the monomers exceptingthe compound (A), 60 to 99% by mole of vinylidene fluoride, 0 to 30% bymole of tetrafluoroethylene and 1 to 10% by mole of hexafluoropropylene,and the like.

Also preferable example of the composition where the prepared polymer isin the form of elastomer is a copolymer comprising 0.01 to 30% by moleof the compound (A) per the total moles of all monomers and, per thetotal moles of the monomers excepting the compound (A), 40 to 90% bymole of vinylidene fluoride, 0 to 30% by mole of tetrafluoroethylene and10 to 50% by mole of hexafluoropropylene.

Examples of the fluorine-containing polymer of the present inventioninclude a segmented fluorine-containing polymer with functional groupobtained by copolymerizing a fluorine-containing olefin (A) withfunctional group when preparing a segmented fluorine-containing polymeras described in JP-B-49327/1986.

That is, the segmented fluorine-containing polymer basically comprises,as the essential components, iodine atom released from an iodidecompound which has iodine atom bonded to carbon atom, a residue of theiodide compound excluding the iodine atom and at least two polymer chainsegments which are present among the iodine atoms and the residues (atleast one of the segments is a fluorine-containing polymer chainsegment). Namely, the segmented fluorine-containing polymer of thepresent invention basically comprises, as the essential components, asequential chain comprising at least 2 polymer chain segments (at leastone of them is a fluorine-containing polymer chain segment); iodine atomreleased from an iodide compound having iodine atom bonded to carbonatom present at one end of the sequential chain; and a residue of theiodide compound after releasing the iodine atom at the other end. Thatis, the typical structure of the segmented fluorine-containing polymerof the present invention is represented by the following formula:

    Q--[(A--B-- . . . )I].sub.f"

wherein Q is a residue of an iodide compound after releasing an iodineatom, A, B, . . . are polymer chain segments (at least one of them is afluorine-containing polymer chain segment), I is iodine atom releasedfrom the above-mentioned iodide compound, f" is the number of bonds ofQ.

The segmented fluorine-containing polymer with functional group preparedby copolymerizing the fluorine-containing olefin (A) with functionalgroup of the present invention is a fluorine-containing copolymerwherein the fluorine-containing olefin (A) with functional group isintroduced through copolymerization to any one of two segments (or threesegments) in the polymer or both segments (two or more segments).

The preferable range of the molecular weight of the fluorine-containingpolymer of the present invention changes depending on kinds, uses andmethods of use of the polymer, and are not limited particularly. Forexample, for application to molding, generally too low molecular weightis not preferable from the viewpoint of mechanical strength of thefluorine-containing polymer or a blended composition of the polymer anda heat-resisting thermoplastic resin. Preferable number averagemolecular weight is usually not less than 2,000, particularly not lessthan about 5,000. Also from the viewpoint of moldability, too highmolecular weight is not preferable. Preferable molecular weight isusually not more than 1,000,000, particularly not more than about750,000.

Among the examples of the fluorine-containing polymers of the presentinvention, in case of resinous copolymers which mainly comprise theabove-mentioned tetrafluoroethylene, for example, melt-processablefluorine-containing polymers such as PFA, FEP and ETFE types comprisingthe fluorine-containing olefin (A) with functional group, their meltflow rates are from 0.01×10⁻² to 50×10⁻² mλ/sec., preferably from0.05×10⁻² to 25×10⁻² mλ/sec., particularly preferably from 0.1×10⁻² to10×10⁻² mλ/sec. at the determined measuring temperature (for example,372° C. in PFA and FEP type polymers and 300° C. in ETFE type polymer)and load (for example, 7 kg) depending on kind of the respectivefluorine-containing resins.

Also among the above-mentioned examples of the polymers of the presentinvention, the number average molecular weight measured by GPC analysisby calibration based on polystyrene is from 2,000 to 1,000,000,preferably from 5,000 to 750,000, particularly preferably from 10,000 to500,000 in case of fluorine-containing polymers soluble in a solventsuch as DMF or THF, e.g. an elastomeric polymer containing the compound(A) and mainly comprising tetrafluoroethylene, a copolymer of thecompound (A) and vinylidene fluoride, and a resinous or elastomericpolymer comprising the compound (A), vinylidene fluoride, and furtherone or more of tetrafluoroethylene, hexafluoroethylene andchlorotrifluoroethylene.

Also, for example, in case of a copolymer of the compound (A) andtetrafluoroethylene, the copolymer includes an oligomer-like polymer, apolymer so-called as a low molecular weight PTFE having a molecularweight of about 2,000 to about 1,000,000 and in addition, a highmolecular weight polymer which is not melt-processable.

In case of the high molecular weight polymer, though the molecularweight cannot be specified, it is from about 1,000,000 to 10,000,000 andabout 20,000,000 at maximum.

The fluorine-containing polymer of the present invention can be preparedin any polymerization method such as suspension polymerization, emulsionpolymerization, solution polymerization and bulk polymerization. Themethod of polymerization can be properly selected depending on mainlykind and use of the polymers.

In case where the copolymer of the present invention is prepared by thesuspension polymerization, the oil-soluble initiator to be used forradical polymerization may be one usually used, and there are, forexample, organic peroxides such as diisopropyl peroxydicarbonate,di-n-propyl peroxydicarbonate and isobutylperoxide; and peroxidesrepresented by the formula: ##STR69## wherein Y³ is hydrogen atom,fluorine atom or chlorine atom, g" is an integer of 2 to 8. Examplesthereof are diperfluoropropionyl peroxide, di(ω-hydroperfluorohexanoyl)peroxide, di(ω-chloroperfluoropropionyl) peroxide and the like. Alsothere are peroxides represented by the formula: ##STR70## wherein h" isan integer of 1 to 10, for example, fluorine type organic peroxides suchas di(trichloroperfluorohexanoyl) peroxide and azo-compounds such asazobisisobutyronitrile.

As the polymerization solvents, there are, for example, water, achlorofluoroalkane and the like, and a mixture of water and thechlorofluoroalkane is preferable.

It is particularly preferable that the chlorofluoroalkane is from 10 to100% by weight based on water from the viewpoints of suspensiondispersibility and economy.

It is preferable to use a chlorofluoroalkane having 1 to about 4 carbonatoms. For example, there are fluoromethanes such asdichlorodifluoromethane, dichloromonofluoromethane,monochlorodifluoromethane, monochlorotrifluoromethane andtetrafluoromethane; fluoroethanes such as tetrafluoroethane,trichlorotrifluoroethane, dichlorotetrafluoroethane andhexafluoroethane; fluoropropanes such as dichloropentafluoropropane;fluorobutanes such as perfluorocyclobutane; and the like. Among them,dichlorotetrafluoroethane, trichlorotrifluoroethane,dichloropentafluoropropane and perfluorocyclobutane are preferably used.

Also as a chain transfer agent, if necessary for molecular weightcontrol, there can be used isopentane, n-hexane, cyclohexane, methanol,ethanol, tert-butanol, carbon tetrachloride, chloroform, methylenechloride, methyl chloride, a fluorocarbon iodide (such as CF₂ I₂, CF₃ I,I--(CF₂)₄ --I or (CF₃)₂ CFI) and the like.

As an initiator to be used in case of preparing the polymers of thepresent invention through the emulsion polymerization, usual radicalinitiators can be used. A water-soluble initiator is used preferably,and examples are a persulfuric acid such as ammonium persulfate salt, aredox initiator which comprises hydrogen peroxide or a combinationthereof with a reducing agent such as sodium hydrogensulfite or sodiumthiosulfate; an inorganic initiator in which a trace amount of iron,ferrous salt, silver sulfate and the like are coexistent with the redoxinitiator; a dibasic acid peroxide such as succinyl peroxide or glutarylperoxide; azobisisobutylamidine dihydrochloric acid; and the like. Alsothe above-mentioned oil-soluble initiators can be used similarly.

As an emulsifying agent, a fluorocarbon type emulsifying agent ispreferably used, and the preferable examples thereof are ammoniumperfluorooctanoate, ammonium perfluorononanoate, an ether typefluorine-containing emulsifying agent represented by the formula:##STR71## and the like. Also, if necessary, a hydrocarbon type anionsurfactant, cation surfactant, nonion surfactant and betaine surfactantcan be used.

Further if necessary, a chain transfer agent similar to one mentionedabove, a pH buffer agent, a pH control agent can also be used.

In case where the polymers of the present invention are prepared by thesolution polymerization, as the polymerizing solvent, in addition to theabove-mentioned chlorofluoroalkanes, there can be used ketones such asacetone, methyl ethyl ketone and methyl isobutyl ketone; esters such asethyl acetate and butyl acetate; aromatic hydrocarbons such as tolueneand xylene; alcohols such as methanol, ethanol and isopropanol; glycolethers such as ethyl cellosolve, monoglyme and diglyme; and the like.

As a polymerization initiator and a chain transfer agent, ones similarto those for the suspension polymerization can be used.

The conditions for polymerization of the polymer of the presentinvention are properly selected depending on kind and composition of thepolymer, reaction method, initiator, reaction medium and the like. Thereaction temperature is usually from -20° to 150° C., preferably from 5°to 100° C., and the polymerization pressure is not more than 100 kgf/cm²G, preferably not more than 50 kgf/cm² G.

In preparing the polymer of the present invention, the method forcharging a polymerization tank with each component (particularlymonomers, an initiator and a chain transfer agent) is not particularlylimited.

A polymerization tank may be initially charged with a whole amount ofeach component to be used at the same time, or may be charged in turnswith a part or the whole of the components continuously or dividedly.

The fluorine-containing polymer of the present invention can beeffectively used for applications which require thermal resistance,chemical resistance, weather resistance, oil resistance, solventresistance and the like as a usual molding material, paint, rubber,adhesive, ion exchange membrane, sealant and the like, in addition tothe use for blending with a heat-resisting thermoplastic resin.

Concretely, the polymer of the present invention can be applied to thefollowing uses, by utilizing the functional group thereof.

1 Among the fluorine-containing monomers (A) with functional group, onehaving hydroxyl group or carboxyl group is introduced into thefluorine-containing resins such as so-called PTFE, FEP, PFA and ETFE togive a modified PTFE, modified FEP, modified PFA and modified ETFE.These polymers can be cross-linked without adding a cross-linking agentby heat-treating at a temperature of not less than 200° C. for at leastone hour, and can provide molded articles which have a high modulus ofelasticity and do not flow even at a temperature of not less than theirmelting point.

In that case, an amount of a fluorine-containing olefin with hydroxylgroup or carboxyl group in the fluorine-containing polymer is from 0.1to 20% by mole. If the concentration of the functional groups is toolow, cross-linking is not sufficient and it becomes difficult to obtaina high modulus of elasticity without using a cross-linking agent. On theother hand, if it is too high, a melting point of thefluorine-containing polymer becomes lowered, and accurate moldingbecomes difficult because it is difficult to maintain the shape of thepolymer during the heat-treatment. Internal strain is easy to occur atthe time of heat-treatment and thus cracking easily occurs. Also it isnot preferable because there occur problems such that thefluorine-containing copolymer becomes in the form of elastomer andmoldability lowers. It is particularly preferable that the polymercontains the fluorine-containing olefin with hydroxyl group or carboxylgroup in a proportion of 0.2 to 10% by mole.

2 A fluorine-containing polymer prepared by introducing thefluorine-containing olefin (A) into a copolymer of tetrafluoroethyleneor chlorotrifluoroethylene and an alkyl vinyl ether or alkyl vinyl esterrepresented by the formula: ##STR72## wherein R¹⁰ is an aliphatic grouphaving 1 to 17 carbon atoms, an alicyclic group having 3 to 17 carbonatoms or a fluoroalkylene group having 1 to 20 carbon atoms, j" is 0 or1, or a vinylidene fluoride type polymer with functional group can be aresin for paints which is excellent in weather resistance, chemicalresistance and antisoil property.

In case where these fluorine-containing resins are used as the paint,there are the following effects of the functional group.

i) It is possible to add a curing agent being capable of reacting withthe functional group of the present invention and to conduct across-linking reaction at normal temperature or with heating. That is,the resin is particularly useful when used as the paint which is curableat normal temperature or with heating, and can form a coating beingexcellent in weather resistance, solvent resistance and antisoilproperty.

The concentration of the functional groups when used as the curablegroups is from 1 to 30% by mole, preferably from 3 to 20% by mole.

The curing agents are optionally selected by considering the functionalgroup in the polymer and are usually polyisocyanates, melamine curingagent, urea resin curing agent, polybasic acid curing agent, epoxycuring agent, polyamine curing agent, polyamide curing agent and thelike.

ii) In case where the paint contains the pigment, introduction of asmall amount of fluorine-containing olefin having carboxyl group amongthe compounds (A) enhances affinity (dispersibility of pigment) betweenthe fluorine-containing polymer and the pigment, and thus can give thecoating being glossy, smooth and excellent in weather resistance. Inthis case, the necessary amount of the carboxyl group-containing monomeris from 0.1 to 5% by mole, and particularly not more than 3% by mole isenough.

iii) In case of aqueous emulsion paint or water-soluble paint,introduction of the carboxyl group-containing monomer of the presentinvention can give dispersion stability in water and water-solubility tothe fluorine-containing polymer.

It is possible to enhance dispersion stability of the aqueous emulsionpaint in water and to give water-solubility as a water-soluble paint byintroducing 0.1 to 10% by mole and 5 to 30% by mole of the carboxylgroup-containing monomers, respectively.

iv) In addition, the introduction of the functional groups of thepresent invention gives various effects such as enhancement of adhesionproperty of the coating to base materials such as metals, woods,concrete and plastics, improvement of solvent solubility of the polymer,and affinity with the curing agent.

3 The elastomeric fluorine-containing polymers with functional group canbe a fluorine-containing rubber being excellent in thermal resistance,chemical resistance, oil resistance, friction property, wear resistanceand cold resistance.

i) In case of using as the fluorine-containing rubber, one of theeffects of introduction of functional groups is, by utilizing thefunctional groups of the present invention as a cross-linking site, toproceed vulcanization easily in a relatively short period of time, andthereby the cross-linked products being excellent in physical propertiessuch as tensile strength, elongation, thermal resistance and compressionset can be obtained.

As a vulcanizing agent, there can be properly selected and used apolyamine compound, a polyol compound, a polycarboxylic acid compound, apolyepoxy compound, a dibasic acid anhydride or a polyfunctional dibasicacid anhydride compound, an ammonium salt of metal oxide, benzoic acid,cuminic acid or higher fatty acid and an amine hydrochloride, dependingon the functional groups in the fluorine-containing elastomer.

ii) In blending a fluorine-containing elastomer and othernon-fluorine-containing elastomer, by using the fluorine-containingelastomer of the present invention which is prepared by introducing afunctional group to a fluorine-containing elastomer and also inaddition, by carrying out the vulcanization in the same manner asmentioned above, there can be obtained excellent physical properties,chemical resistance, flexibility and low temperature property whichcould not be found on the conventional fluorine-containing elastomer.

As the above-mentioned non-fluorine-containing elastomer, there arepreferably acryl type, silicone type, epichlorohydrine type, NBR typeand urethane type elastomers.

Also, when selecting a functional group of the fluorine-containingelastomer, kind of the non-fluorine-containing elastomer, a vulcanizingagent and a vulcanizing method and controlling a vulcanization rate ofeach elastomer and a cross-linking density, co-crosslinking of a systemof a fluorine-containing elastomer with functional group and anon-fluorine-containing elastomer can be carried out and a cross-linkedblended composition being excellent in mechanical strength andcompression set can be obtained. The concentration of the functionalgroups is from 0.01 to 10% by mole, preferably from 0.1 to 5% by molewhen cross-linking or blending and co-crosslinking with the othernon-fluorine-containing elastomer by using the functional groups of theabove-mentioned fluorine-containing elastomer with functional group.

The third invention of the present inventions relates to thethermoplastic resin composition comprising the above-mentionedfluorine-containing polymer with functional group and a heat-resistingthermoplastic resin.

That is, the thermoplastic resin composition of the present inventioncomprises a composition blended by mixing

(D) 0.1 to 99% (% by weight, hereinafter the same) of thefluorine-containing polymer with functional group and

(E) 1 to 99.9% of the heat-resisting thermoplastic resin having amelting point of crystal or glass transition point of not less than 150°C., and as the fluorine-containing polymer (D) with functional group,one or more selected from the fluorine-containing polymers described inthe present application are used.

It is possible to provide a composition capable of easily givinghomogeneous molded articles which could not be obtained by conventionalmethods, by using the fluorine-containing polymer with functional groupof the present invention at the time of blending the heat-resistingthermoplastic resin and the fluorine-containing polymer.

The fluorine-containing polymer (D) with functional group is thefluorine-containing polymer of the present invention The functionalgroup in the fluorine-containing polymer with functional group isselected mainly depending on kind of the heat-resisting thermoplasticresin (E) to be blended, and there are preferably used thefluorine-containing polymers with hydroxyl group, carboxyl group, acarboxylester group and glycidyl group, which are highly reactiveparticularly with the thermoplastic resin (E).

The concentration of the functional groups in the fluorine-containingpolymer (D) with functional group can be freely selected depending onkind of the thermoplastic resin (E), a ratio of (D) to (E), purpose anduse. However the excessive concentration of the functional groups is notdesirable from the viewpoint of the properties of the composition suchas thermal resistance, chemical resistance and mechanical properties.The concentration may be as minimum as necessary for improving thedispersion when blending with the thermoplastic resin. The content ofthe fluorine-containing monomer (A) with functional group is preferablyfrom 0.01 to 30% by mole, particularly preferably from 0.05 to 15% bymole on the basis of all monomers used in the fluorine-containingpolymer (D) with functional group.

The fluorine-containing polymer (D) with functional group can beproperly selected depending on kind of the heat-resisting thermoplasticresin (E) to be used, and use and purpose of the composition or moldedarticles, and preferable polymer (D) is to comply with the followingrequirements.

1) Many of the heat-resisting thermoplastic resins (E) are usuallymelted and kneaded at a temperature of 200° to 380° C. It is preferablethat in order to obtain good dispersion, the fluorine-containing polymer(D) is melted at a temperature of not more than 380° C., particularlynot more than 350° C., and thereby the thermoplastic resin and thekneading temperature at the time of blending can be selected from a widerange.

2) It is necessary that the fluorine-containing polymer (D) itself hasthermal stability (thermal resistance) in kneading and molding at a hightemperature. A slight decomposition of the polymer at kneading isunavoidable as far as its effect can be observed. The thermal resistanceshould be 200° C. at lowest, preferably not less than 250° C. Thethermal resistance mainly depends on kind and ratio of monomers to beused. In case where hydrocarbon type monomers, for example, alkyl vinylether, alkyl vinyl ester and allyl compounds, excepting ethylene,propylene and isobutylene, are used, it is preferable that the contentof the monomers in these polymers is limited to not more than 20% bymole, and particularly the content of not more than 10% by mole isrecommendable.

The thermal resistance of the present invention is evaluated by atemperature at which the weight decreases by 1% when measuring with athermobalance (heating up at 10° C./min) in air.

3) It is necessary that the fluorine-containing polymer itself has ahigh chemical resistance, oil resistance and solvent resistance and hascapability of giving such properties to a composition prepared byblending with the thermoplastic resin (E).

As the fluorine-containing polymer (D) preferable for satisfying theabove-mentioned requirements, the first ones are the fluorine-containingcopolymers with functional group mainly comprising tetrafluoroethylene(or chlorotrifluoroethylene), and among them, ones prepared byintroducing a functional group-containing monomer to so-called FEP, PFAand E(C)TFE are preferable, and particularly preferable are PFA andE(C)TFE type fluorine-containing copolymers with functional group. Themost preferable one is an ethylene-tetrafluoroethylene (orchlorotrifluoroethylene) type copolymer.

The second preferable fluorine-containing polymers (D) are vinylidenefluoride type fluorine-containing polymers with functional group,particularly the polymer in which a functional group is introduced toPVdF and the polymer wherein a functional group is introduced to thecopolymer mainly comprising vinylidene fluoride. Particularly preferableare the fluorine-containing polymer of PVDF type and thefluorine-containing copolymer with functional group which have thecomposition including vinylidene fluoride-tetrafluoroethylene copolymer,vinylidene fluoride-tetrafluoroethylene-chlorotrifluoroethylenecopolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylenecopolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer orvinylidene fluoride-hexafluoropropylene copolymer.

The fluorine-containing polymer with functional group of the presentinvention may be in any form of resin and elastomer depending on kindand ratio of monomers to be used. The difference between the resin andthe elastomer only means that the latter has a glass transitiontemperature lower than room temperature, and either of them can beselected depending on the purpose of blending. In case of enhancingimpact resistance of the thermoplastic resin and preparing anelastomeric blended composition, an elastomeric fluorine-containingpolymer with functional group is used.

Among the fluorine-containing polymers (D) of the present invention, themost preferable fluorine-containing elastomers with functional group,which can achieve the above-mentioned purposes, are thefluorine-containing copolymer mainly comprising tetrafluoroethylene andthe fluorine containing copolymer mainly comprising vinylidene fluoride.

The molecular weight of the fluorine-containing polymer with functionalgroup of the present invention is equivalent to those of usualfluorine-containing resin and fluorine-containing elastomer exceptingPTFE which has a high molecular weight of not less than severalmillions. The number average molecular weight is 2,000 to 1,000,000. Toolow molecular weight impairs thermal resistance of the composition andlowers mechanical properties depending on a proportion of thecomposition On the other hand, too high molecular weight lowersmoldability and thus is not preferable. The preferable number averagemolecular weight is from about 5,000 to about 750,000, particularlypreferable is from about 10,000 to about 500,000.

In the present invention, the fluorine-containing polymer (D) withfunctional group is blended with the thermoplastic resin (E) having amelting point of crystal or glass transition temperature of not lessthan 150° C. As the thermoplastic resin, there are, for example,polyacetal, polyamide, polycarbonate, poly(phenylene ether), aromaticpolyester, aromatic polyesteramide, aromatic azomethine, poly(arylenesulfide), polysulfone, poly(ether sulfone), polyketone, poly(etherketone), poly(ether imide), polyamide imide, polymethylpentene,poly(ether nitrile) and the like.

Among them, preferable resins are as follows:

1) Thermoplastic resin (E) itself having an excellent thermalresistance. It is necessary not to lower thermal stability of thecomposition when blending with the fluorine-containing polymer.

Though the thermoplastic resin (E) having an excellent thermalresistance is used, when usual modifiers and additives are used forimproving impact resistance and chemical resistance, the compositionlowers in thermal resistance. Therefore a fluorine-containing polymerhaving an excellent thermal resistance is desired.

2) Thermoplastic resin being excellent in mechanical strength anddimensional stability and being capable of modifying those of thefluorine-containing resin.

3) Thermoplastic resin which is excellent in moldability and can giveexcellent processability to the composition prepared by blending with afluorine-containing polymer.

Preferable examples are, for instance, aromatic polyester, polyamide,polyamide imide, poly(arylene sulfide), polyketone, poly(ether nitrile),polycarbonate, poly(phenylene ether), polysulfone, poly(ether imide),polyimide and the like.

Particularly preferable examples are the poly(arylene sulfide) which isstrongly desired to be improved in impact resistance without impairingthermal resistance and chemical resistance; the polyamide which isdesired to be improved in solvent resistance, particularly gasoholresistance when used as materials for automobile parts; and the aromaticpolyester which is expected to enhance moldability and mechanicalproperties of the fluorine-containing polymer by the addition Amongthem, there is particularly preferably a liquid crystal polyesterforming an anisotropic melt because of its high modulus of elasticity,excellent molding processability and dimensional stability. Whenenhancing compatibility with the fluorine-containing polymer, the liquidcrystal polyester is expected to considerably enhance mechanicalproperties, moldability, dimensional stability and deflectiontemperature under load of the fluorine-containing polymer.

On the other hand, in case of considering reactivity of thefluorine-containing polymer (D) with functional group of the presentinvention with the thermoplastic resin (E), the poly(phenylene sulfide)has a thiolate group (or thiol group), the polyamide has amino group,carboxyl group and amide bond, and the aromatic polyester has hydroxylgroup, carboxyl group and ester bond, and thus these resins arepreferable because such functional groups are highly reactive with thefunctional groups in the fluorine-containing polymer (D).

The functional groups of the fluorine-containing polymer (D) withfunctional group of the present invention are hydroxyl group, carboxylgroup, carboxylester group and glycidyl group. These functional groupsare in general highly reactive with the ester bond in the trunk chainand hydroxyl group and carboxyl group at the chain end in case where theheat-resisting thermoplastic resin (E) is the aromatic polyester; theamide bond in the trunk chain and amino group and carboxyl group at thechain end in case of polyamide (PA); and the thiolate group (or thiolgroup) at the chain end in case of poly(arylene sulfide). That is, thecomposition prepared by melting and kneading the fluorine-containingpolymer (D) with functional group and the thermoplastic resin (E) ispresumed to be present in any form of

(1) a reaction product resulting from a reaction between the functionalgroup of the fluorine-containing polymer (D) with functional group and apart of the trunk chain and/or chain end(s) of the thermoplastic resin(E),

(2) a composition obtained by a chemical reaction between a part of thefluorine-containing polymer (D) and a part of the thermoplastic resin(E) in the same manner as in (1), wherein the resulting reaction productacts as a compatibilizing agent for the composition containing unreactedpolymers, and

(3) a composition wherein interfacial affinity and interfacialadhesivity of the fluorine-containing polymer with the thermoplasticresin (E) are improved by introducing the functional group to thefluorine-containing polymer even without causing a chemical reaction.

As mentioned above, though a mechanism of giving a mutual excellentdispersibility by blending the fluorine-containing polymer (D) withfunctional group and the thermoplastic resin (E) is not clear, this doesnot restrict the present invention.

The modification of the thermoplastic resin (E) by usual methods inorder to enhance affinity and reactivity with the fluorine-containingpolymer with functional group of the present invention also is notexcluded from the scope of the present invention.

Also the resin composition of the present invention can comprise apolymer component (F) other than the thermoplastic resin (E) and thefluorine-containing polymer (D) with functional group.

The preferable component as (F) is a fluorine-containing polymer havingno functional group, which is defined by excluding thefluorine-containing monomer (A) with functional group and otherfunctional group-containing monomers from the fluorine-containingpolymer as described in the present application. The particularlypreferable examples of (F) are as follows:

(1) PTFE (including copolymers comprising less than 1% by weight of afluorine-containing olefin copolymerizable with TFE) and perfluoro typefluorine-containing resins or elastomers such as TFE/perfluoro(alkylvinyl ether) copolymer (PFA), TFE/HFP copolymer (FEP) andTFE/perfluoro(alkyl vinyl ether)/HFP terpolymer,

(2) resinous copolymers commonly known as ETFE or ECTFE, wherein a molarratio of ethylene to TFE and/or CTFE is 2:3 to 3:2 and a thirdfluorine-containing monomer copolymerizable therewith is contained in anamount of 0 to 15% by mole on the basis of the total amount of ethyleneand TFE and/or CTFE monomers; or elastomeric copolymers comprising about40 to about 90% by mole of ethylene, about 0.1 to about 20% by mole ofTFE and/or CTFE and about 10 to about 60% by mole of a thirdfluorine-containing monomer, wherein as the third fluorine-containingmonomer, there is used at least one represented by CH₂ ═CZ⁷ (CF₂)_(k")Z⁸ (Z⁷ is H or F, Z⁸ is H or F, k" is an integer of 1 to 10), CF₂═CF(CF₂).sub.λ" Y⁴ (Y⁴ is H or F, λ" is an integer of 1 to 10), CF₂═CFO(CF₂)_(m") Y⁵ (Y⁵ is H or F, m" is an integer of 1 to 6) or CH₂═C(CF₃)₂ ; and tetrafluoroethylene/propylene copolymer, for example,elastomeric copolymer comprising 40 to 70% by mole oftetrafluoroethylene and 30 to 60% by mole of propylene,

(3) PVDF and VDF type copolymers (resinous or elastomeric copolymers ofVDF and at least one selected from fluorine-containing olefins such asTFE, CTFE, HFP, CH₂ ═C(CF₃)₂ or (CF₃)₂ C═O), wherein VDF/HFP copolymer,VDF/CTFE copolymer and VDF/TFE/HFP or CTFE terpolymer become elastomersusually when VDF is in the range of about 20 to about 80% by mole andTFE is in the range of less than about 40% by mole, HFP is about 10 toabout 60% by mole and CTFE is about 15 to about 40% by mole, and

(4) as the other polymers, fluorine-containing resins or elastomers suchas polychlorotrifluoroethylene (PCTFE) and poly(fluoroalkylα-substitutedacrylate) wherein the substituent is hydrogen atom, methyl,fluorine atom or chlorine atom.

Namely, in the composition comprising three components, i.e. thefluorine-containing polymer (D) with functional group, the thermoplasticresin (E) and the above-mentioned fluorine-containing polymer (F)without functional group, the reaction products resulting from thereaction of the fluorine-containing polymer (D) with functional groupand a part of the thermoplastic resin (E) can function as acompatibilizing agent between the fluorine-containing polymer (F) andthe remaining portion of the thermoplastic resin (E). In other words, inblending the fluorine-containing polymer (F) and the thermoplastic resin(E), by adding and melt-blending the fluorine-containing polymer (D)with functional group, the compatibilizing agent is formed in thecomposition, and the composition can obtain dispersibility, mechanicalproperties, chemical resistance and the like which cannot be obtained bya simple blend of the fluorine-containing polymer (F) and thethermoplastic resin (E).

Accordingly as the fluorine-containing polymer (D) with functionalgroup, which is added for improving dispersibility in theabove-mentioned compositions, one having a high compatibility with thefluorine-containing polymer (F) without functional group is preferable.

For example, it is most preferable, from a point of an effect ofimproving dispersibility, to add the fluorine-containing polymer withfunctional group prepared by introducing the functional group to thecomposition selected from the perfluoro type fluorine-containing resinsor elastomers of the above (1) in case where the thermoplastic resin (E)is blended with the fluorine-containing polymer similarly selected fromthe perfluoro type fluorine-containing resins or elastomers of the above(1) as the fluorine-containing polymer (F); the fluorine-containingpolymer prepared by introducing the functional group to the compositionselected from the group of (2), i.e. ethylene/tetrafluoroethylene (orchlorotrifluoroethylene) type polymer and propylene/tetrafluoroethylenecopolymer, in case where the thermoplastic resin (E) is blended with thefluorine-containing polymer (F) which is selected similarly from thegroup (2); and the fluorine-containing polymer selected from thefluorine-containing polymers with functional group which mainly comprisevinylidene fluoride, in case where the fluorine-containing polymer (F)is selected from the group of the vinylidene fluoride type polymers ofthe above (3) and is blended with (E).

An amount of the fluorine-containing polymer (D) with functional group,which is effective for enhancing dispersibility in blending thefluorine-containing polymer (F) and the thermoplastic resin (E), variesdepending on kind, blending ratio, purpose of each of thefluorine-containing polymer (F) and the thermoplastic resin (E), andusually and sufficiently effective is from 0.5 to 50% by weight,preferably from 0.5 to 30% by weight on the basis of the whole amount ofthe composition, and particularly from 1 to 20% by weight.

It is necessary that the three components, i.e. the fluorine-containingpolymer (D) with functional group, the thermoplastic resin (E) and thefluorine-containing polymer (F) without functional group, are blended atleast under melting and fluidized state at a temperature of not lessthan the melting point of crystal or glass transition temperature of thethermoplastic resin. It is desirable that during the blending, thefluorine-containing polymer with functional group is also in the moltenstate, but for the reason of high melt viscosity or cross-linkingproperty, the polymer may keep non-melting state.

The thermoplastic resin composition of the present invention is oneprepared by mixing the fluorine-containing polymer (D) with functionalgroup and the thermoplastic resin (E) having a melting point of crystalor glass transition temperature of not less than 150° C., and thecontent of (D) is from 0.1 to 99% and (E) is from 1 to 99.9%.

In case where (D) is from 0.1 to 40% and (E) is from 60 to 99.9%, theproperties such as impact resistance, sliding property, chemicalresistance and moldability which are drawbacks of many of thethermoplastic resins, can be enhanced by the fluorine-containingpolymer. Also in case of 40 to 99% of (D) and 1 to 60% of (E),properties of the fluorine-containing polymer such as strength,deflection temperature under load, moldability and dimensional stabilitycan be enhanced by the thermoplastic resin. In case where in the weightratio of the resin composition, (D) is less than 0.1% and (E) is lessthan 1%, the above-mentioned enhancing effect becomes unsatisfactory.

The content and kind of the fluorine-containing polymer with functionalgroup in the composition vary depending on kind and concentration of thefunctional group, main components and molecular weight of the polymer,and therefore are not equally determined and are selected according tokind of the thermoplastic resin to be blended in the above-mentionedrange and purpose of the blending.

The preferable resin composition of the present invention is onecomprising the fluorine-containing polymer having hydroxyl group,carboxyl group or glycidyl group and the poly(arylene sulfide),polyamide, aromatic polyester or polycarbonate.

Poly(arylene sulfide) is excellent in thermal resistance and mechanicalproperties, but inferior particularly in impact resistance. In blendingpoly(arylene sulfide) and the fluorine-containing polymer (D) withfunctional group, it is preferable, for enhancing dispersibility, to usethe fluorine-containing polymers (D) having hydroxyl group and havingglycidyl group which are highly reactive with a thiolate group (or thiolgroup) at the chain end of poly(phenylene sulfide). Among them,elastomeric fluorine-containing polymer is particularly preferable forenhancing impact resistance.

The concentration of the functional groups in the fluorine-containingelastomer varies depending on kind and mixing ratio of thefluorine-containing elastomer and the poly(arylene sulfide), and is from0.01 to 30% by mole, preferably from 0.01 to 20% by mole, particularlypreferably from about 0.05 to about 10% by mole per the number of molesof the monomers used in the fluorine-containing elastomer.

Preferable examples of the functional group-containing elastomer areelastomers having hydroxyl group or glycidyl group as the functionalgroup among the vinylidene fluoride type fluorine-containing polymers,or elastomers having hydroxyl group or glycidyl group as the functionalgroup among the fluorine-containing polymers mainly comprisingtetrafluoroethylene. Among these polymers, particularly preferable arevinylidene fluoride-hexafluoropropylene copolymer, vinylidenefluoride-tetrafluoroethylene-hexafluoropropylene copolymer andtetrafluoroethylene-propylene copolymer, to which hydroxyl group orglycidyl group is introduced.

As PPS used in the present invention, there is no restriction if it isprepared by the known method as mentioned in JP-B-3368/1970, and PPScontaining 70% by mole or more of the recurring unit shown by theformula: ##STR73## is preferable. Further there is used particularlypreferably PPS having the poly(phenylene sulfide) unit of not less than70% by mole. At that time, there is no restriction on the residualrecurring units if they are copolymerizable. Examples are o-phenylenesulfide unit, m-phenylene sulfide unit, diphenyl sulfide ether unit,diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit, biphenylsulfide unit, naphthalene sulfide unit, trifunctional phenylene sulfideunit and the like. These copolymers may be block-copolymerized orrandom-copolymerized.

Examples of the preferred PPS are poly(p-phenylene sulfide),poly(p-phenylene sulfide)-poly(m-phenylene sulfide) block copolymer,poly(p-phenylene sulfide)-polysulfone block copolymer andpoly(p-phenylene sulfide)-polyphenylene sulfide sulfone copolymer.

Structure of PPS may be a straight chain type, a cross-linked type withoxygen in coexistence with oxygen, a heat-treated type under inert gasatmosphere and an admixture of these structures.

Also a functional group having high reactivity may be introduced to PPSto further enhance the compatibility with the fluorine-containingpolymer with functional group of the present invention. As thefunctional group to be introduced, amino group, carboxyl group, hydroxylgroup and the like are suitable. As the introducing methods, there are amethod in which a halogenated aromatic compound with functional group iscopolymerized, a method in which the functional group is introduced bypolymer reaction of PPS with a low molecular weight compound withfunctional group, and the like.

The above-mentioned PPS may be one which is reduced in sodium ioncontent by deionization treatment (acid cleaning and hot water cleaningor the like).

The fluorine-containing elastomer with functional group and poly(arylenesulfide) can be used in the range of 0.1 to 40% and 60 to 99.9%,respectively, particularly preferably 5 to 30% and 70 to 95%. In casewhere the fluorine-containing elastomer with functional group is lessthan 5%, impact resistance cannot be improved sufficiently, andcontrarily when more than 30%, mechanical strength lowers remarkably.

The composition which comprises the poly(phenylene sulfide) prepared inthe manner mentioned above and the fluorine-containing polymer withfunctional group can give the molded articles excellent mechanicalproperties, particularly an excellent impact resistance, which cannot beobtained by simply blending the fluorine-containing polymer withoutfunctional group.

Also since the thermoplastic resin composition has thermal resistance,chemical resistance and sliding property which are inherent to thefluorine-containing polymer and also the thermal resistance andmechanical properties which are inherent to poly(phenylene sulfide), thecomposition is useful particularly as a molding material for electricaland electronic parts by utilizing its thermal resistance and electricalproperties; for automobile parts by utilizing its sliding property; forpipes and valves for chemical plant and gear parts for pumps byutilizing its chemical resistance; and the like.

Polyamide resins have a high strength, high toughness and excellentprocessability and are used widely for hoses, tubes, pipes and the like.On the other hand, though they are usually excellent in oil resistance,they are poor in resistance to an alcohol type solvent. In case wheregasoline containing a lower alcohol is used, oil resistance (gasoholresistance) is worse to swell in volume and to increase fuelpenetration, which causes deterioration of materials such as decrease instrength.

The composition having the improved solvent resistance and gasoholresistance of the polyamide resin can be prepared by blending thefluorine-containing polymer (D) with functional group of the presentinvention with the polyamide resin or by adding the fluorine-containingpolymer (D) with functional group to a blended composition of thefluorine-containing polymer (F) and the polyamide resin.

As the fluorine-containing polymer (D) with functional group in thecomposition comprising the polymer (D) and polyamide, preferable is thefluorine-containing polymer with carboxyl group or thefluorine-containing polymer with glycidyl group, in view of highreactivity to any of amide bond of the trunk chain of polyamide or aminogroup or carboxyl group at the chain end(s). The concentration of thefunctional groups varies depending on kind, mixing ratio and purpose ofthe fluorine-containing polymer and polyamide resin, and is preferablyfrom 0.01 to 30% by mole, more preferably from 0.01 to 20% by mole,particularly preferably from about 0.05 to about 10% by mole per thenumber of moles of the fluorine-containing polymer.

As the fluorine-containing polymer (D) with functional group, either ofresinous or elastomeric polymer can be selected depending on the purposeand use. In case of resinous fluorine-containing polymers, there is norestriction if they are capable of heat-melting. Among them, thefluorine-containing polymers having a relatively low melting point, thatis, a melting point of not more than 300° C., particularly not more than280° C. are especially preferable to prevent thermal deterioration ofpolyamide in the composition when preparing the composition by meltingand kneading with polyamide. Concretely the ethylene-tetrafluoroethylene(or chlorotrifluoroethylene) copolymers with carboxyl group or glycidylgroup and the vinylidene fluoride type polymers with carboxyl group orglycidyl group are preferable. Particularly preferable vinylidenefluoride type polymers are PVDF, and the copolymers such as vinylidenefluoride-tetrafluoroethylene copolymer, vinylidenefluoride-hexafluoropropylene copolymer, vinylidenefluoride-chlorotrifluoroethylene copolymer, vinylidenefluoride-tetrafluoroethylene-hexafluoroethylene copolymer and vinylidenefluoride-tetrafluoroethylene-chlorotrifluoroethylene copolymer, to eachof which carboxyl group or glycidyl group is introduced.

Also preferable elastomeric fluorine-containing polymers are thecopolymers with carboxyl group and glycidyl group, which comprise mainlytetrafluoroethylene, and the vinylidene fluoride copolymers.

Also the composition having the improved dispersibility and chemicalresistance can be obtained by adding the fluorine-containing polymer (D)with functional group when blending the fluorine-containing polymer (F)without functional group and the polyamide resin. Examples of thecompositions are a composition prepared by adding the polymer havingcarboxyl group or glycidyl group to a blend of ETFE (or ECTFE) andpolyamide; a composition prepared by adding the polymer which hascarboxyl group or glycidyl group and is selected from the vinylidenefluoride type polymers, to a blend of PVDF and polyamide resin; and acomposition prepared by adding the polymer which has carboxyl group orglycidyl group and is selected from the vinylidene fluoride typepolymers, to a blend of polyamide and the resinous or elastomericvinylidene fluoride type polymer comprising vinylidene fluoride as theessential component and at least one selected from tetrafluoroethylene,hexafluoropropylene and chlorotrifluoroethylene.

In case of a composition prepared by adding the fluorine-containingpolymer (D) with functional group to a blend of polyamide and thefluorine-containing polymer (F) without functional group, the content of(D), which is effective for enhancing dispersibility and compatibility,varies depending on kind, mixing ratio and the like of thefluorine-containing polymer (F) and polyamide, and is usually from 0.5to 50%, preferably from 0.5 to 30%, particularly preferably from 1 to20% on the basis of the whole amount of the composition.

As the polyamide resins, there can be usually used ones prepared bycondensation of a linear diamine represented by the following formula:

    H.sub.2 N--(CH.sub.2).sub.p" --NH.sub.2

wherein p" is an integer of 3 to 12, and a linear carboxylic acidrepresented by the following formula:

    HO.sub.2 C--(CH.sub.2).sub.q" --CO.sub.2 H

wherein q" is an integer of 2 to 12, and ones prepared throughring-opening polymerization of lactam. Examples of the preferablepolyamides are nylon 66, nylon 610, nilon 612, nylon 46, nylon 34, nylon69, nylon 6, nylon 12, nylon 11, nylon 4 and the like. Also there can beused copolymerized polyamides such as nylon 6/610, nylon 6/612, nylon6/46, nylon 6/12, nylon 6/66, nylon 6/66/610, nylon 6/46/66, nylon6/66/612, nylon 6/46/610 and nylon 6/46/12.

Also there can be used nylon 6/6T (T is a terephthalic acid component),semi-aromatic polyamides obtained from an aromatic dicarboxylic acidsuch as terephthalic acid or isophthalic acid and meta-xylene diamine oran alicyclic diamine, and polyamides obtained from meta-xylene diamineand the above-mentioned linear carboxylic acid.

The compositions as mentioned above, which comprise thefluorine-containing polymer (D) with functional group and polyamide, andthe compositions prepared by adding the fluorine-containing polymer (D)with functional group to the blend of the fluorine-containing polymer(F) without functional group and polyamide can give molded articleshaving an excellent chemical resistance, impact resistance at lowtemperature and mechanical properties which cannot be obtained by simplyblending the fluorine-containing polymer without functional group. Thesecompositions are useful as materials having an excellent chemicalresistance and impermeability, particularly against reformate gasolinecontaining an alcohol (for example methanol, ethanol and the like) ormethyl t-butyl ether and an acid. Therefore, the compositions are usefulfor molded articles such as hoses, tubes, pipes, sealings, gaskets,packings, sheets and films. Also the compositions can be materialsuseful for automobile parts which require chemical resistance andimpermeability against gasoline and methanol-mixed gasoline, e.g. hoses,tubes, gaskets and the like for fuel piping.

Perfluoro type fluorine-containing resins such as PTFE, FEP and PFA andfluorine-containing resins such as ETFE, ECTFE, PVDF and vinylidenefluoride type copolymers (for example, vinylidenefluoride-tetrafluoroethylene copolymer and the like) are in generalexcellent in thermal resistance, chemical resistance, weatherresistance, electrical properties and the like, but in many cases areinferior in mechanical properties, physical thermal resistance shown bydeflection temperature under load, dimensional stability and the like ascompared with crystalline heat-resisting thermoplastic resins.

There can be obtained the composition in which mechanical properties,deflection temperature under load and dimensional stability of thefluorine-containing resin are improved by using the fluorine-containingresin (D) with functional group of the present invention in place of theconventional fluorine-containing resins, by blending the heat-resistingthermoplastic resins (E), particularly aromatic polyester orpolycarbonate, or by adding the fluorine-containing polymer (D) withfunctional group when blending the conventional fluorine-containingresin (F) and the aromatic polyester or polycarbonate.

As the fluorine-containing polymer (D) in the composition comprising thearomatic polyester or polycarbonate and the fluorine-containing polymer(D) with functional group, the polymers having hydroxyl group,carboxylester group or glycidyl group are preferable. Among them,particularly preferable are fluorine-containing polymers having hydroxylgroup or carboxylester group which is seemed to be easily subjected totransesterification with the ester group at the trunk chain of thearomatic polyester or the carbonate group at the trunk chain ofpolycarbonate. The proportion of the hydroxyl group, carboxylester groupor glycidyl group varies depending on kind of the aromatic polyester andpolycarbonate, kind of the fuorine-containing polymer and compositionratio, and is from 0.01 to 30% by mole, preferably from 0.01 to 20% bymole, particularly from about 0.05 to about 10% by mole per the totalamount of the fluorine-containing polymer with functional group.

In case of the composition comprising two components, i. e. afluorine-containing polymer with functional group and the aromaticpolyester or polycarbonate, various fluorine-containing polymers withfunctional group can be selected depending on purpose and use, andpreferable are polymers such as PTFE, FEP, PFA, ETFE, ECTFE, PVdF,vinylidene fluoride type copolymer resin (VdF-TFE copolymer and thelike) and PCTFE, to which hydroxyl group or carboxylester group isintroduced Among them, particularly preferable are PFA, ETFE, ECTFE,PVdF and PCTFE to which hydroxyl group or carboxylester group isintroduced. The mechanical properties, deflection temperature underload, dimensional stability and moldability of each correspondingfluorine-containing resin can be effectively improved.

In the composition comprising two components, i.e. thefluorine-containing polymer (D) with functional group and the aromaticpolyester or polycarbonate, the proportions effective for improvingmechanical properties, deflection temperature under load, dimensionalstability and moldability are from 50 to 99% of the fluorine-containingpolymer (D) with functional group and 1 to 50% of the aromatic polyesteror polycarbonate (E), preferably 60 to 97% of (D) and 3 to 40% of (E).

In case of the composition comprising three components in which thefluorine-containing polymer (D) with functional group of the presentinvention is added at the time of the blending of the conventionalfluorine-containing resin (F) and the aromatic polyester orpolycarbonate, there is preferably selected the fluorine-containingpolymer (D) with functional group having good compatibility with thefluorine-containing resin (F) without functional group in thecomposition As the examples of the composition, particularly preferableare a composition prepared by adding the fluorine-containing polymer,which is obtained by introducing hydroxyl group or carboxylester groupto the polymer selected from perfluoro type fluorine-containing resins(for example, PTFE, FEP, PFA and the like), to a blend of the perfluorotype fluorine-containing resin and the aromatic polyester orpolycarbonate; a composition prepared by adding theethylene/tetrafluoroethylene (or chlorotrifluoroethylene) copolymer withhydroxyl group or carboxylester group, to a blend of ETFE (or ECTFE) andthe aromatic polyester or polycarbonate; and a composition prepared byadding the vinylidene fluoride type polymer (in this case, either of theresinous or elastomeric polymer may be used) with hydroxyl group orcarboxylester group, which is selected from polymers mainly comprisingvinylidene fluoride to a blend of PVdF or the vinylidene fluoride typecopolymer resin and the aromatic polyester or polycarbonate.

In the composition prepared by adding the fluorine-containing polymer(D) with functional group to the blend of the conventionalfluorine-containing resin and the aromatic polyester or polycarbonate,the content of the above-mentioned (D), which is effective for enhancingdispersibility and compatibility, varies depending on kind and mixingratio of the fluorine-containing resin, aromatic polyester andpolycarbonate, and is usually from 0.5 to 50%, preferably from 0.5 to30%, particularly preferably from 1 to 20% on the basis of the wholeamount of the composition

In the composition of three components prepared by adding thefluorine-containing polymer (D) with functional group to the blend ofthe fluorine-containing resin (F) and the aromatic polyester orpolycarbonate (E), the proportion effective for improving mechanicalproperties, deflection temperature under load, dimensional stability andmoldability of the fluorine-containing polymer is 0.5 to 50% of thefluorine-containing polymer (D) with functional group, 1 to 50% of thearomatic polyester or polycarbonate (E) and remaining amount of thefluorine-containing resin (F) (provided that the sum of (D) and (F) is50 to 99%), preferably 1 to 30% of (D), 3 to 40% of (E) and remainingamount of (F) (provided that the sum of (D) and (F) is 60 to 97%).

When the elastomeric fluorine-containing polymer is used as thefunctional group-containing polymer (D) of the present invention and ismelt-blended with the thermoplastic resin (E), a chemical reactionoccurs partly, and a thermoplastic elastomer composition can be obtainedin a specific composition ratio of (D) to (E). Specifically bymelt-blending the aromatic polyester or polycarbonate with thefluorine-containing polymer with functional group of the presentinvention, particularly a fluorine-containing elastomer with hydroxylgroup or carboxylester group in a specific composition ratio thereof,the transesterification occurs partly and there can be obtained athermoplastic elastomer composition having flowability at a hightemperature as a thermoplastic resin and rubber elasticity as anelastomer. In this thermoplastic elastomer composition, as the elastomerwith hydroxyl or carboxylester group, there are particularly preferablyused a polymer mainly comprising tetrafluoroethylene and a polymermainly comprising vinylidene fluoride. The content of hydroxyl group orcarboxylester group is from 0.01 to 30% by mole, preferably from 0.01 to20% by mole, particularly preferably from 0.05 to 10% by mole on thebasis of the whole monomers of the fluorine-containing elastomer.

In mixing the aromatic polyester or polycarbonate and thefluorine-containing elastomer with hydroxyl group or carboxylestergroup, the mixing ratio thereof, which can endow the elastomericcomposition with flowability at a high temperature and rubber elasticityas a thermoplastic elastomer, is from 50 to 99.9% of thefluorine-containing elastomer with hydroxyl group or carboxylester groupand 0.1 to 50% of the aromatic polyester or polycarbonate, particularlypreferably 70 to 98% and 2 to 30%, respectively. Also thermoplasticelastomers having various hardness can be prepared by selecting themixing ratio in the above range.

The use of polycarbonate is extending to the fields of automobiles andbuilding because of their characteristics such as mechanical strength,impact resistance and weather resistance, but they are inferior inchemical resistance, particularly alkali resistance and solventresistance.

The composition having more effectively improved chemical resistancewithout remarkably lowering mechanical properties can be obtained byblending the fluorine-containing polymer with hydroxyl group among thefluorine-containing polymers with functional group of the presentinvention and polycarbonate in the same manner as in case of improvingchemical resistance of the polyamide.

As the aromatic polyester used in the composition of the presentinvention, there are condensation products of a dibasic acid such asadipic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid or4,4'-biphenyldicarboxylic acid and a dihydric alcohol such as ethyleneglycol, trimethylene glycol, tetramethylene glycol, pentamethyleneglycol, hexamethylene glycol, 1,4-cyclohexanedimethanol or bisphenol A(for example, polyethylene terephthalate, polybutylene terephthalate,poly-1,4-cyclohexanedimethylene terephthalate,poly[2,2-propanebis(4-phenyltere/isophthalate)] and the like); aromaticpolyesters (liquid crystal copolyester) forming an anisotropic melt; andthe like.

Also the polycarbonate used in the composition of the present inventionis obtained by a reaction of a bisphenol compound and phosgene or adiester carbonate. As the bisphenol compound,2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "bisphenolA") is particularly preferable, and a part or the whole of bisphenol Amay be substituted by other bisphenol compounds. As the bisphenolcompounds other than bisphenol A, there are, for example, hydroquinone,resorcin, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane,bis(4-hydroxyphenyl) cycloalkane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone,bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, or analkyl-substituted product, an aryl-substituted product or ahalogen-substituted product thereof and the like.

Among them, the liquid crystal polyester itself is, because of itsorientation, most excellent in mechanical properties such as strengthand modulus of elasticity, in thermal properties such as deflectiontemperature under load and in dimensional stability, and shows a highflowability at the time of melting. Further the liquid crystal polyesterorientates in the composition by melt-blending with other polymers, andthus can endow the composition with similar excellent characteristics asmentioned above. Therefore the polyester can be used most preferably forpreparing a composition having the improved mechanical properties,deflection temperature under load, dimensional stability and moldabilityof the fluorine-containing resin and the thermoplastic elastomericcomposition. As the liquid crystal polyester used in the presentinvention, there are, for example, liquid crystal copolyesterscomprising the components selected from one or more of aromaticdicarboxylic acids and alicyclic dicarboxylic acids, one or more ofaromatic diols, alicyclic diols and aliphatic diols and one or more ofaromatic hydroxycarboxylic acids. As the represented combinationsthereof, there are, for example, polyesters mainly comprisingpara-hydroxybenzoic acid, biphenyl diol and terephthalic acid (forexample, ECONOL E2000, E6000 or E7000 available from Sumitomo ChemicalCo., Ltd., Xydar RC/FC400, 300 available from Nippon Petrochemicals Co.,Ltd., VECTRA C Series available from Polyplastics Co., Ltd., UENOLCP2000 available from Ueno Fine Chemical Co., Ltd. and IDEMITSU LCP300available from Idemitsu Petrochemicals Co., Ltd.; polyesters mainlycomprising para-hydroxybenzoic acid and 6-hydroxynaphthoic acid (forexample, VICTREX SRP available from ICI Japan Ltd., UENO LCP1000available from Ueno Fine Chemical Co., Ltd., VECTRA A Series availablefrom Polyplastics Co., Ltd., NOVACCURATE E324 available from MitsubishiChemical Corp., IDEMITSU LCP 300 available from Idemitsu PetrochemicalsCo., Ltd., and LODRUN LC-5000 available from Unitika Ltd.); polyestersmainly comprising para-hydroxybenzoic acid, terephthalic acid and analiphatic diol (for example, NOVACCURATE E310 available from MitsubishiChemical Corp., IDEMITSU LCP100 available from Idemitsu PetrochemicalsCo., Ltd., LODRUN LC-3000 available from Unitika Ltd. and X7G availablefrom Eastman Kodak Corp.); and the like.

In case where the thermoplastic elastomer composition is prepared byblending the fluorine-containing elastomer with functional group of thepresent invention and the above-mentioned liquid crystal polyester, itis preferable to use a liquid crystal copolyester mainly comprising6-hydroxynaphthoic acid and para-hydroxybenzoic acid having a relativelylow melting temperature or a liquid crystal copolyester mainlycomprising para-hydroxybenzoic acid, terephthalic acid and aliphaticdiol in consideration of thermal resistance of the fluorine-containingelastomer with functional group.

Among the fluorine-containing thermoplastic resin compositionscomprising the aromatic polyester or polycarbonate of the presentinvention which are prepared in the above manner, the compositions whichhave the improved mechanical properties, deflection temperature underload, dimensional stability and moldability of the fluorine-containingresin, have, in addition thereto, excellent thermal resistance, chemicalresistance and electrical properties which are inherent to thefluorine-containing resin. As a result, the composition can beparticularly useful materials for electrical and electronic parts whichrequire dimensional stability, thermal resistance and electricalproperties, for example, connectors, chips, carriers, receptacles,printed board, covering material for wire and the like; chemicallyresistive parts relating to semiconductor production, particularly largesize wafer baskets which are difficult to be produced from thefluorine-containing resin solely due to lack of moldability andstrength, or valves and parts for chemical pumps; machine parts such asfuel-related parts for automobiles, gears and bearings, which requirethermal resistance and sliding property; and the like.

The thermoplastic elastomer composition comprising the above-mentionedfluorine-containing elastomer with hydroxyl group or carboxylester andthe aromatic polyester or polycarbonate is one in which thefluorine-containing elastomer component forms a continuous phase by achemical bond between a part of the aromatic polyester or polycarbonategiving flowability at high temperature to the composition and a part ofthe fluorine-containing elastomer being capable of giving rubberelasticity through the functional groups of the fluorine-containingelastomer. Accordingly the composition of the present invention isexcellent in thermal resistance and chemical resistance as compared withthe conventional elastomeric thermoplastic composition prepared bydynamically vulcanizing a fluorine-containing elastomer into athermoplastic resin so that the thermoplastic resin forms a continuousphase. Also since the composition of the present invention can beprepared only by melt-blending without using any vulcanizing agent andadditive, the lowering of chemical resistance due to those impuritiesand the contamination due to their elusion can be prevented.

Also the composition of the present invention has, of course,moldability in injection molding and recycling capability asthermoplastic elastomers.

Accordingly the elastomeric thermoplastic composition of the presentinvention is a useful material for uses in the field of medicine andbiochemistry such as for tubes, plugs of drug bottles, gaskets andinjectors; in the field of semiconductor industry such as for tubes, Orings and sealants; in the field of electrics and electronics such asfor heat insulating coatings of wires and sealants; in the field of foodindustry such as for hoses and sealants; in the field of automobileindustry such as for fuel hoses, tubes, gaskets, equal velocity jointboots and rack and pinion boots; in the field of chemical industry suchas for pressure-resistance hoses, diaphragms, packings, gaskets andhoses; in the field of building industries such as for sealants; and thelike.

Further the resin composition of the present invention may contain, asfar as its effect is not impaired, organic or inorganic fillers to beused usually, for example, fibrous reinforcements such as glass fiber,carbon fiber, aramide fiber, graphite whisker, potassium titanatewhisker, basic magnesium sulfate whisker, magnesium whisker, magnesiumborate whisker, calcium carbonate whisker, calcium sulfate whisker, zincoxide whisker, aluminium borate whisker, alumina whisker, siliconcarbide whisker, silicon nitride whisker, wollastonite, xonotlite,sepiolite, gypsum fiber and slag fibers; inorganic fillers such ascarbon powder, graphite powder, calcium carbonate powder, talc, mica,clay and glass beads; heat-resisting resins such as polyimide; andfurther solid lubricants such as molybdenum disulfide, colorants andretarders, and the content thereof is usually from 1 to 30% on the basisof the whole amount of the composition. There is a case where an effectof the addition is far more enhanced because of the presence ofunreacted functional groups contained in the resin composition of thepresent invention.

As the melting and mixing machines used in the present invention, thereare a mixing roll, Banbury mixer, Brabender mixer, an extrusion machineand the like, and among them, an extrusion machine is preferable fromthe points that kneading power is large and the dispersibility isexpected to be enhanced more at blending and also that productivity isexcellent in the production of the composition. As the extrusionmachine, there can be used ones of uniaxial screw or biaxial screw typeor ones having more than two screws, and the biaxial screw typeextrusion machine is particularly preferable from the points that thecompositions having good dispersibility can be obtained because oflarger kneading power and that the kneading power can be optionallycontrolled.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is a graph showing measurements of surface tension of EXAMPLES 11and 12.

FIG. 2 is a scanning type electron microscope photograph of a cutsurface of the molded article obtained in EXAMPLE 55.

FIG. 3 is a scanning type electron microscope photograph of a cutsurface of the molded article obtained in EXAMPLE 56.

FIG. 4 is a scanning type electron microscope photograph of a cutsurface of the molded article obtained in COMPARATIVE EXAMPLE 10.

FIG. 5 is a scanning type electron microscope photograph of a cutsurface of the molded article obtained in COMPARATIVE EXAMPLE 11.

FIG. 6 is a stress-strain curve in the tensile tests of the moldedarticles obtained in EXAMPLES 66 to 68 and COMPARATIVE EXAMPLE 22.

BEST MODE FOR CARRYING OUT THE INVENTION

Synthesis of the fluorine-containing olefin and fluorine-containingpolymer of the present invention and production of the thermoplasticresin composition using the fluorine-containing polymer are explainedbelow on the basis of EXAMPLES, but the present invention is not limitedthereto.

I. Examples relating to the fluorine-containing monomer with functionalgroup

In the following examples, abbreviations and symbols mentioned below areused.

R-11: Trichlorofluoromethane

NMR: Nuclear magnetic resonance spectrum

IR: Infrared absorption spectrum

MS: Mass spectrum

REFERENCE EXAMPLE 1

2,2-difluoro-3-iodopropionyl fluoride (ICH₂ CF₂ COF)

A three-liter four-necked flask was charged with 1,500 mλ of tetraglyme,and 825 g of sodium iodide was completely dissolved with stirring atroom temperature. Subsequently with feeding water to a cooler, 650 g of2,2,3,3-tetrafluorooxetane was added slowly and dropwise at a reactiontemperature ranging from 30° to 40° C., and the addition was completedin 45 minutes.

The titled compound, i.e. 2,2-difluoro-3-iodopropionyl fluoride of 1,050g was recovered by distilling the reaction mixture under reducedpressure of 30 mmHg at 38° to 40° C. Boiling point: 95° to 96° C.

REFERENCE EXAMPLE 2

Synthesis of methylperfluoro(6,6-dihydro-6-iodo-2trifluoromethyl-3-oxahexanoate)

(ICH₂ CF₂ CF₂ OC(CF₃)FCOOCH₃)

A two-liter four-necked flask was charged with 43 g of cesium fluoride,6 mλ of tetraglyme and 400 g of 2,2-difluoro-3-iodopropionyl fluorideprepared in REFERENCE EXAMPLE 1, and the inside temperature was adjustedto 10° C. with stirring. Subsequently after introducinghexafluoropropylene oxide from a gas bomb into the flask for 21 hours ata reflux speed through a dry ice cooler, 300 mλ of methanol was addedwith cooling by iced water. After rinsing the reaction product withwater several times, there was obtained, through distillation, thetitled compound, i.e. methylperfluoro(6,6-dihydro-6iodo-2-trifluoromethyl-3-oxahexanoate). Yield:250 g, boiling point: 116° to 117° C. (60 mmHg).

REFERENCE EXAMPLE 3

Synthesis of methylperfluoro(9,9-dihydro-9-iodo-2,5bistrifluoromethyl-3,6-dioxanonanoate)

(ICH₂ CF₂ CF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOOCH₃)

A two-liter four-necked flask was charged with 60 g of cesium fluoride,10 mλ of tetraglyme and 600 g of 2,2-difluoro-3-iodopropionyl fluorideprepared in REFERENCE EXAMPLE 1, and the inside temperature was adjustedto 10° C. with stirring. Subsequently after introducinghexafluoropropylene oxide from a gas bomb into the flask for 30 hours ata reflux speed through a dry ice cooler, 500 mλ of methanol was addedwith cooling by iced water. After rinsing the reaction product withwater several times, there was obtained, through distillation, thetitled compound, i.e. methylperfluoro(9,9-dihydro-9iodo-2,5-bistrifluoromethyl-3,6-dioxanonanoate).Yield: 116 g, boiling point: 100° to 101° C.(15 mmHg).

REFERENCE EXAMPLE 4

Synthesis of methylperfluoro(12,12-dihydro-12-iodo-2,5,8-tristrifluoromethyl-3,6,9-trioxadodecanoate)

(ICH₂ CF₂ CF₂ OC(CF₃)FCF₂ OC(CF₃)FCF₂ OC(CF₃)FCOOCH₃)

After rinsing, with water, the reaction product prepared in the samemanner as in REFERENCE EXAMPLE 3, the titled compound, i.e. methylperfluoro(12,12,-dihydro-12-iodo-2,5,8-tristrifluoromethyl-3,6,9-trioxadodecanoate)was obtained through distillation. Yield: 85 g, boiling point: 105° to106° C.(2 mmHg).

EXAMPLE 1

Synthesis of methylperfluoro(6,6-dihydro-2-trifluoromethyl-3-oxa-5-hexenoate)

(CH₂ =CFCF₂ OC(CF₃)FCOOCH₃)

A one-liter four-necked flask equipped with a stirrer, cooler anddropping funnel was charged with 500 mλ of methanol and 84.6 g of zincpowder, and the inside temperature was adjusted to 60° to 65° C. Withstirring, 270 g of methylperfluoro(6,6-dihydro-6-iodo-2trifluoromethyl-3-oxahexanoate) preparedin REFERENCE EXAMPLE 2 was added dropwise for about one hour through thedropping funnel. Further after stirring at 65° to 68° C. for one hour,the inside temperature was cooled to room temperature.

The reaction mixture was filtrated to separate excessive zinc, and thenpoured into 1 liter of IN hydrochloric acid. After allowed to stand, anorganic layer was collected, rinsed with water, dried and then distilledto obtain the titled compound, i.e. methylperfluoro(6,6-dihydro-2-trifluoromethyl-3-oxa-5hexenoate). Yield: 171.9g, boiling point: 72° to 73° C. (95 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.55 to 5.38 (2H, m), 4.06 (3H, s.br.).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -70.8 to -71.5 (1F, m), -77.5 to -78.1 (1 F, m), -82.3 (3 F, s.br.), -124.2 to -124.5 (1F, m), -131.3 to -131.4 (1 F, m).

IR(cm⁻¹): 1787 (ν c=o), 1695 (ν c=c).

MS(m/e): 270 (P), 159 (C--(CF₃)FCOOCH₃), 95 (CH₂ ═CFCF₂), 69 (CF₃), 59(COOCH₃), 15 (CH₃).

EXAMPLE 2

Synthesis of perfluoro(6,6-dihydro-2-trifluoromethyl-3-oxa-5-hexenoicacid)

(CH₂ ═CFCF₂ OC--(CF₃)FCOOH)

A 500 mλ four-necked flask equipped with a stirrer, cooler and droppingfunnel was charged with 17.1 g of sodium hydroxide and 300 mλ ofmethanol to dissolve them completely, and the inside temperature waskept at room temperature. With stirring, 100 g of methylperfluoro-(6,6-dihydro-2-trifluoromethyl-3-oxa-5hexenoate) prepared inEXAMPLE 1 was added dropwise for about 30 minutes through the droppingfunnel, and further after stirring at room temperature for one hour, thesolution was poured into 1 liter of 2N hydrochloric acid. After allowedto stand, an organic layer was collected, rinsed with water, dried andthen distilled to obtain the titled compound, i.e.perfluoro(6,6-dihydro-2-trifluoromethyl-3-oxa-5-hexenoic acid). Yield:50.5 g, boiling point: 81° to 82° C. (20 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 11.5 (1H, s.br.), 5.50 to 5.37 (2H, m).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -70.5 to -71.3 (1F, m), -77.2 to -77.8 (1 F, m), -82.4 (3 F, m), -124.1 to -124.4 (1 F,m), -131.3 to -131.5 (1 F, m).

IR(cm⁻¹): 3511 (ν non-associated OH), 2655 to 3300 (ν associated OH),1771 (ν c=o), 1695 (ν c=c).

MS(m/e): 256 (P), 145 (C--(CF₃)FCOOH), 95 (CH₂ ═CFCF₂), 69 (CF₃), 45(COOH).

EXAMPLE 3

Synthesis ofperfluoro(1,1,6,6-tetrahydro-2-trifluoromethyl-3-oxa-5-hexenol)

(CH₂ ═CFCF₂ OC--(CF₃)FCH₂ OH)

A three-liter four-necked flask equipped with a stirrer, cooler anddropping funnel was charged with 416 g of methylperfluoro(6,6-dihydro-6-iodo-2-trifluoromethyl-3-oxahexanoate) obtainedin REFERENCE EXAMPLE 2 and 500 mλ of ethanol, and the inside temperaturewas kept at 0° to 5° C. With stirring, the solution prepared bydissolving 26.5 g of sodium boron hydride (NaBH₄) in 600 mλ of ethanolwas added dropwise for about 4 hours through the dropping funnel, andduring the addition, the inside temperature was kept at 0° to 10° C.

Further after stirring at 0 to 10° C. for two hours, the reactionmixture was slowly poured into 3 liters of 1N-hydrochloric acid. Afterallowed to stand, an organic layer was collected, rinsed with water,dried and then distilled to obtain 281 g ofperfluoro(1,1,6,6-tetrahydro-6-iodo-2-trifluoromethyl-3-oxa-hexanol)(ICH₂ CF₂ CF₂ OC--(CF₃)FCH₂ OH). Boiling point: 75° to 77° C. (5 mmHg).

A 500 mλ four-necked flask equipped with a stirrer, cooler and droppingfunnel was charged with 59.2 g of zinc powder and 200 mλ of methanol,and the inside temperature was kept at 60° to 65° C. With stirring, 271g of the above-mentioned reduced alcohol was added dropwise for aboutone hour. After completion of the addition, further heating at 60° to65° C. for one hour followed.

The reaction mixture was treated in the same manner as in EXAMPLE 1 toobtain the titled compound, i.e.perfluoro(1,1,6,6-tetrahydro-2-trifluoromethyl-3-oxa-5-hexenol). Yield:103 g, boiling point: 76° to 77° C. (95 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.47 to 5.30 (2H, m), 5.15 (1H, t.J=6.3Hz), 4.28 to 4.19 (2H, m).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -71.7 to -72.3 (1F, m), -73.1 to -73.7 (1 F, m), -81.5 (3 F, s.br), -123.2 to -123.5 (1F, m), -134.3 to -134.5 (1 F, m).

IR(cm⁻¹): 3631 (ν non-associated OH), 3411 (ν associated OH), 1695 (νc=c).

MS(m/e): 242 (P), 131 (C--(CF₃)FCH₂ OH), 95 (CH₂ ═CFCF₂), 69 (CF₃), 31(CH₂ OH).

EXAMPLE 4

Synthesis of methylperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoate)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC(CF₃)FCOOCH₃)

A two-liter four-necked flask equipped with a stirrer, cooler anddropping funnel was charged with one liter of methanol and 127 g of zincpowder, followed by a reaction with 873 g of methylperfluoro(9,9-dihydro-9iodo-2,5-bistrifluoromethyl-3,6-dioxanonanoate)prepared in REFERENCE EXAMPLE 3 in the same manner as in EXAMPLE 1 at63° to 68° C. After the reaction, the mixture was treated in the samemanner as in EXAMPLE 1 to obtain the titled compound, i.e. methylperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoate).Yield: 482 g, boiling point: 70° to 71° C.(16 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.32 to 5.16 (2H, m, J_(HF) =47.6, 16.8Hz), 3.49 (3H, s.br.).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -73.9 to -74.4 (2F, m), -79.1 to -80.0 (1 F, m), -80.6 (3 F, m), -83.1 (3 F, m), -86.3 to-86.8 (1 F, m), -123.2 to -123.6 (1 F, m, J_(HF) =47.6, 16.8 Hz), -132.3to -132.7 (1 F, m), -146.3 to -146.8 (1 F, m).

IR(cm⁻¹): 1790 (νc=o), 1695 (νc=c).

MS(m/e): 436 (P), 325 (P--CF₂ ═CFCF₂ O), 159 (C--(CF₃)FCOOCH₃), 95 (CH₂═CFCF₂), 69 (CF₃), 59 (COOCH₃), 15 (CH₃).

EXAMPLE 5

Synthesis ofperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoic acid)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOOH)

A two-liter four-necked flask equipped with a stirrer, cooler anddropping funnel was charged with 43 g of sodium hydroxide and 700 mλ ofmethanol to dissolve them completely. Afterwards, 403 g of methylperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoate)prepared in EXAMPLE 4 was subjected to hydrolysis reaction in the samemanner as in EXAMPLE 2, and then treated in the same manner as inEXAMPLE 2 to give the titled compound, i.e.perfluoro-(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoicacid). Yield: 332 g, boiling point: 79° to 80° C. (0.12 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 12.5 (1H, s.br.), 5.60 to 5.30 (2H, m).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -72.7 to -73.0 (2F, m), -78.2 to -79.2 (1 F, m), -79.7 (3 F, m), -82.3 (3 F, m), -84.1 to-85.0 (1 F, m), -124.1 to -124.4 (1 F, m), -131.1 to -131.3 (1 F, m),-145.3 to -145.7 (1 F, m).

IR(cm⁻¹): 3520 (ν non-associated OH), 2650 to 3300 (ν associated OH),1772 (ν c=o), 1694 (ν c=c).

MS(m/e): 442 (P), 311 (C--(CF₃)FCH₂ C(CF₃)FCOOH), 95 (CH₂ =CFCF₂), 69(CF₃), 45 (COOH).

EXAMPLE 6

Synthesis ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCH₂ OH)

Reducing reaction and isolation of methylperfluoro(9,9-dihydro-9-iodo-2,5-bistrifluoromethyl-3,6dioxanonanoate)of 582 g, which was obtained in REFERENCE EXAMPLE 3, were carried out inthe same manner as in EXAMPLE 3 by using sodium boron hydride (NaBH₄),to give 365 g ofperfluoro(1,1,9,9-tetrahydro-9-iodo-2,5-bistrifluoromethyl-3,6-dioxanonanol)(ICH₂ CF₂ CF₂ OC(CF₃)FCF₂ OC--(CF₃)FCH₂ OH). Boiling point: 65° to 66°C. (0.4 mmHg).

Subsequently, de-IF reaction and isolation were carried out in the samemanner as in EXAMPLE 3 by using 305 g of the reduced alcohol obtained asmentioned above and 46.5 g of zinc powder, to give the titled compound,i.e.perfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol).Yield: 351.2 g, boiling point: 77° to 78° C. (14 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.31 to 5.12 (2H, m), 4.19 to 4.12 (2H, m),2.80 (1H, m).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -74.3 to -74.6 (2F, m), -80.2 to -80.7 (1 F, m), -81.0 (3 F, m), -82.1 to -82.9 (1 F, m),-83.3 (3 F, m), -123.6 to -124.1 (1 F, m), -137.1 to -137.4 (1 F, m),-146.3 to -146.5 (1 F, m).

IR(cm⁻¹): 3630 (ν non-associated OH), 3405 (ν associated OH), 1699 (νc=c).

MS(m/e): 408 (P), 261 (CH₂ ═CFCF₂ OC--(CF₃)CF), 131 (C--(CF₃)FCH₂ OH),95 (CH₂ ═CFCF₂), 69 (CF₃), 31 (CH₂ OH).

EXAMPLE 7

Synthesis of methylperfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOOCH₃)

De-IF reaction in methanol and then isolation were carried out in thesame manner as in EXAMPLE 2 by using 187 g of methylperfluoro(12,12-dihydro-12-iodo-2,5,8-tristrifluoromethyl-3,6,9-trioxadodecanoate)prepared in REFERENCE EXAMPLE 4 and 21.2 g of zinc powder, to give thetitled compound, i.e. methylperfluoro(12,12dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate).Yield: 96.3 g, boiling point: 117° to 118° C. (20 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.55 (1H, dd, J=15.6, 4.7 Hz), 5.46 (1H,dd, J=42.9, 4.7 Hz), 4.12 (3H, S).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -72.8 to -73.3 (2F, m), -78.4 to -79.4 (2 F, m), -79.6 to -80.1 (6 F, m), -82.2 to -82.4(3 F, m), -84.2 to -85.3 (2 F, m), -124.2 to -124.7 (1 F, m), -131.0 to-131.3 (1 F, m), -145.0 to -145.5 (2 F, m).

IR(cm⁻¹): 1791 (ν c=o), 1696 (ν c=c).

MS(m/e): 602 (P), 491 (P--CH₂ ═CFCF₂), 427 (P--OC--(CF₃)FCOOCH₃), 325(C--(CF₃)FCF₂ OC--(CF₃)FCOOCH₃), 261 (CH₂ ═CFCF₂ OC--(CF₃)FCF₂), 159(C--(CF₃)FCOOCH₃), 95 (CH₂ ═CFCF₂), 69 (CF₃), 59 (COOCH₃), 15 (CH₃).

EXAMPLE 8

Synthesis ofperfluoro(12,12-dihydro-2,5,8tristrifluoromethyl-3,6,9-trioxa-11-dodecenoicacid)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOOH)

Hydrolysis reaction and isolation of 90.3 g of methylperfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate)prepared in EXAMPLE 7 in the same manner as in EXAMPLE 2 by usingmethanol solution containing 7.6 g of sodium hydroxide were carried outto give the titled compound, i.e.perfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoicacid). Yield: 59.0 g, boiling point: 110° to 112° C. (0.15 mmHg).

¹ H-NMR: δ (ppm) 11.72 (1H, br.s.), 5.55 to 5.30 (2H, m).

¹⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -72.8 to -73.4 (2F, m), -78.5 to -79.5 (2 F, m), -79.6 to -80.5 (6 F, m), -82.4 to -82.7(3 F, m), -83.9 to -85.6 (2 F, m), -124.1 to -124.5 (1 F, m), -130.8 to-131.4 (1 F, m), -145.1 to -145.6 (2 F, m).

IR(cm⁻¹): 3533 (ν non-associated OH), 2650 to 3300 (ν associated OH),1779 (ν c=o), 1696 (ν c=c).

MS(m/e): 588 (P), 427 (P--OC--(CF₃)FCOOH), 261 (CH₂ ═CFCF₂ OC--(CF₃)FCF₂--), 95 (CH₂ ═CFCF₂), 69 (CF₃), 45 (COOH).

EXAMPLE 9

Synthesis of ammoniumperfluoro(9,9-dihydro-2,5bistrifluoromethyl-3,6-dioxa-8-nonenoate)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOONH₄)

A small amount ofperfluoro(9,9-dihydro-2,5bistrifluoromethyl-3,6-dioxa-8-nonenoic acid)prepared in EXAMPLE 5 was dissolved in ethanol, followed byneutralization titration with 0.1N-KOH/ethanol standard solution byusing a potentiometric titration equipment. Then the number of baseequivalents necessary for neutralizing 1 g of the above-mentionedcarboxylic acid was measured, and was 2.42×10⁻³ equivalents.

Subsequently 19.2 g of the same carboxylic acid compound as above wasdissolved and neutralized in 46.5 mλ of 1.0N-ammonia water, withmeasuring its concentration through titration, and the solution wasintroduced to a 200 mλ measuring flask and water was added to give asolution amounting to 200 mλ. Thus 10% (wt/vol) aqueous solution of thetitled compound, i.e. ammoniumperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoate) wasobtained.

A part of this solution was vacuum-dried repeatedly at 80° C. to give awhite solid.

¹ H-NMR: δ (ppm) (in D₂ O), 5.41 to 5.14 (2H, m), 4.96 to 4.72 (4H, dr.s.).

¹⁹ F-NMR: δ (ppm) (in D₂ O, R-11 internal standard), -73.9 to -74.4 (2F, m), -80.7 to -81.0 (3 F, m), -81.0 to -82.6 (2 F, m), -83.1 to -83.3(3 F, m), -125.2 to -125.5 (1 F, m), -126.7 to -127.0 (1 F, m), -146.3to -146.8 (1 F, m).

IR(cm⁻¹, KBr method): 3590 to 2700 (ν N--H), 1688 (ν c=c), 1664 (ν c=o).

EXAMPLE 10

Synthesis of ammoniumperfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate)

(CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOONH₄)

In the same manner as in EXAMPLE 9, 19.4 g ofperfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9trioxa-11-dodecenoicacid) prepared in EXAMPLE 8 was mixed with 31.0 mλ of 1N ammonia waterto be neutralized, and then the whole of the solution was diluted withwater to be 200 mλ to give 10% (wt/vol) aqueous solution of the titledcompound, i.e. ammoniumperfluoro(12,12-dihydro-2,5,8-tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate).

A part of this solution was vacuum-dried repeatedly at 80° C. to give awhite solid.

¹ H-NMR: δ (ppm) (in D₂ O), 5.26 to 5.00 (2H, m), 4.92 to 4.74 (4H, br.s.).

¹⁹ F-NMR: δ (ppm) (in D₂ O, R-11 internal standard), -79.5 to -86.5 (4F, m), --81.0 to -82.5 (6 F, m), -83.0 to -84.0 (3 F, m), -124.5 to-126.0 (1 F, m), -127.0 to -128.0 (1 F, m), -146.8 to -148.0 (2 F, m).

IR (cm⁻¹): 3560-2730 (ν N--H), 1694 (ν c=c), 1661 (ν c=o).

EXAMPLE 11

Use of ammoniumperfluoro(9,9-dihydro-2,5bistrifluoromethyl-3,6-dioxa-8-nonenoate) as anemulsifying agent (measurement of critical micelle concentration(hereinafter referred to as cmc))

Ten % aqueous solution of the above-mentioned ammonium salt prepared inEXAMPLE 9 was diluted further with water to prepare solutions havingdifferent concentrations, and each surface tension was measured. Theresults are shown in FIG. 1.

The cmc read from FIG. 1 was 59.2 mmol/liter.

EXAMPLE 12

Use of ammoniumperfluoro(12,12-dihydro-2,5,8tristrifluoromethyl-3,6,9-trioxa-11-dodecenoate)as an emulsifying agent (Measurement of cmc)

Surface tensions were measured in the same manner as in EXAMPLE 11except that the ammonium salt synthesized in EXAMPLE 10 was used insteadof the ammonium salt prepared in EXAMPLE 9. The results are shown inFIG. 1.

From FIG. 1, cmc was 8.3 mmol/liter.

The results in FIG. 1 indicate that the respective ammonium saltsobtained in EXAMPLES 9 and 10 have a good surface activity and can beused as a reactive emulsifying agent.

EXAMPLE 13

Synthesis of2,3,3,5,6,6,8-heptafluoro-4,7,10-trioxa-5,8-bistrifluoromethyl12,13-epoxytridecane-1-ene##STR74##

A 300 mλ four-necked flask equipped with a stirrer and cooler wascharged with 62.6 g ofperfluoro-(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)prepared in EXAMPLE 6 and 70.6 g of epichlorohydrin, and heated to 80°C. Then 7.8 g of sodium hydroxide was dividedly added three times overabout 30 minutes. During adding, the inside temperature was kept at 80°to 90° C. After stirring at 80° C. for 30 minutes, the mixture wascooled to room temperature.

The reaction mixture was introduced into 500 mλ of pure water, and afterallowed to stand, an organic layer was collected, rinsed with water,dried and distilled to give the titled compound, i.e.2,3,3,5,6,6,8heptafluoro-4,7,10-trioxa-5,8-bistrifluoromethyl-12,13epoxytridecane-1-ene.Yield: 46.8 g, boiling point: 78° to 80° C. (0.2 mmHg).

¹ H-NMR: δ (ppm) (in CDCl₃), 5.63 to 5.37 (2H, m), 4.40 to 4.19 (2H, m),4.05 to 3.95 (1H, m), 3.59 to 3.48 (1H, m), 3.20 to 3.09 (1H, m), 2.81to 2.72 (1H, m), 2.64 to 2.54 (1H, m).

⁹ F-NMR: δ (ppm) (in CDCl₃, R-11 internal standard), -72.6 to -73.0 (2F, m), -79.4 to -79.6 (3 F, m), -79.1 to -80.2 (1 F, m), -80.7 to -81.6(1 F, m), -82.0 to -82.2 (3 F, m), -124.0 to -124.4 (1 F, m), -132.8 to-133.2 (1 F, m), -145.1 to -145.6 (1 F, m).

IR(cm⁻¹): 1695 (ν c=c). ##STR75## II. Examples of fluorine-containingpolymer with functional group

The following abbreviations are used for the fluorine-containing monomer(A) with functional group and other copolymerizing monomer (B), whichare used in the present invention

N-0-OH: CH₂ ═CFCF₂ OC--(CF₃)FCH₂ OH (described in EXAMPLE 3)

N-1-OH: CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCH₂ OH (described in EXAMPLE6)

N-0-COOH: CH₂ ═CFCF₂ OC--(CF₃)FCOOH (described in EXAMPLE 2)

N-1-COOH: CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOOH (described in EXAMPLE5)

N-2-COOH: CH₂ ═CFCF₂ O--[C--(CF₃)FCF₂ O]₂ --OC--(CF₃)FCOOH (described inEXAMPLE 8)

N-1-COONH₄ : CH₂ ═CFCF₂ OC--(CF₃)FCF₂ OC--(CF₃)FCOONH₄ (described inEXAMPLE 9) ##STR76## (described in EXAMPLE 13) TFE: Tetrafluoroethylene

VdF: Vinylidene fluoride

HFP: Hexafluoropropylene

CTFE: Chlorotrifluoroethylene

PPVE: Perfluoro(propyl vinyl ether)

PMVE: Perfluoro(methyl vinyl ether)

E: Ethylene

Also for the following examples, the abbreviations, symbols and wordsmentioned below are used.

As catalysts,

IPP: Diisopropyl peroxydicarbonate

NPP: Di-n-propyl peroxydicarbonate

APS: Ammonium persulfate.

As emulsifying agents,

PFOA: Perfluoro octanoic acid ammonium (C₇ F₁₅ COONH₄).

As solvents,

R-141b: 1,1-dichloro-1-fluoroethane,

R-113: 1,1,2-trichloro-1,2,2-trifluoroethane,

R-114: 1,2-dichloro-1,1,2,2-tetrafluoroethane,

THF: Tetrahydrofuran,

DMF: Dimethylformamide.

For measurement and analysis,

DSC: Differential scanning calory measurement,

Tg: Glass transition temperature,

Tm: Melting point,

Td: Thermal decomposition temperature (assumed to be a temperature atwhich weight decreases by 1% in air. The temperature at which weightdecreases by 1% in air at a heat-up rate of 10° C./min was measured byusing a thermal analyser, model DT-30 available from ShimadzuCorporation),

GPC molecular weight: Molecular weight measured by gel permeationchromatograph analysis, which is calculated on the basis of polystyrene(by using THF solvent or DMF solvent),

Mn: Number average molecular weight,

Mw: Weight average molecular weight,

Flow rate: After preheating for 5 minutes, a volume per unit time(mλ/sec) of a copolymer flowing through a 2 mm diameter and 8 mm longnozzle was measured by using a flow tester, and the measured value is aflow rate.

EXAMPLE 14

Copolymerization ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)and tetrafluoroethylene

A 250 mλ autoclave equipped with a valve, pressure gauge and thermometerwas charged with 16.3 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6dioxa-8-nonenol)prepared in EXAMPLE 6, 60 g of 1,1-dichloro-1-fluoroethane (R-141b) and0.10 g of diisopropyl peroxydicarbonate (IPP) as shown in TABLE 1, andwas cooled with dry ice/methanol solution. Then the inside of the systemwas replaced by nitrogen sufficiently. Afterwards 6.3 g oftetrafluoroethylene (TFE) was fed through the valve to react at 45° C.for 20 hours with shaking.

                  TABLE 1                                                         ______________________________________                                        Reaction conditions                                                                      Ex. 14  Ex. 15  Ex. 16                                                                              Ex. 17                                                                              Ex. 18                                 ______________________________________                                        Functional group-                                                                        N-1-OH  N-1-OH  N-1-OH                                                                              N-0-OH                                                                              N-1-COOH                               containing monomer                                                            (A)                                                                           Charged amount (g)                                                                       16.3    2.4     20.4  1.1   2.6                                    Monomer (B)                                                                   Charged amount                                                                TFE (g)    6.3     --      --    --    --                                     VdF (g)    --      4.5     4.5   6.9   9.4                                    Initiator  IPP     IPP     IPP   IPP   IPP                                    Charged amount (g)                                                                       0.10    0.08    0.13  0.12  0.16                                   Solvent    R-141b  R-141b  R-141b                                                                              R-113 R-113                                  Charged amount (g)                                                                       60      60      60    40    40                                     Reaction   45      45      45    45    45                                     temperature (° C.)                                                     Reaction time (hr)                                                                       20      20      20    17    19                                     ______________________________________                                    

With proceeding of the reaction, the gauge pressure before the reaction,i.e. 4.3 kg/cm² G decreased to 2.1 kg/cm² G. After discharging theun-reacted monomer, the precipitated solid was taken out, dissolved inacetone and precipitated again by using hexane to separate thecopolymer. Vacuum drying was carried out until reaching a constantweight, and 4.1 g of the copolymer was obtained.

The composition of the obtained copolymer was confirmed by ¹ H-NMR and¹⁹ F-NMR analysis, and the presence of the functional groups by infraredabsorption spectrum.

Also the molecular weight of the copolymer was measured by GPC which wascalculated on the basis of polystyrene, the glass transition temperature(Tg) by DSC, and the thermal decomposition temperature bythermogravimetric measurement. The results are shown in TABLE 2.

EXAMPLES 15 TO 18

Copolymerization of fluorine-containing monomer with functional groupand vinylidene fluoride

Copolymers were obtained in the same manner as in EXAMPLE 14 except thatthe monomers, initiators and solvents (and weights thereof) were changedto those described in TABLE 1.

After completion of the reaction, the copolymers of EXAMPLES 15 and 16were separated in the same manner as in EXAMPLE 14, and the copolymersof EXAMPLES 17 and 18 were obtained by rinsing the obtained white powderwith water, cleaning with methanol and then vacuum-drying. The resultsof measuring the yield, composition by NMR analysis, thermal analysis(Tg, Tm, Td) and molecular weight of each copolymer are shown in TABLE2.

                  TABLE 2                                                         ______________________________________                                        Results                                                                       of polymerization                                                                        Ex. 14  Ex. 15  Ex. 16                                                                              Ex. 17                                                                              Ex. 18                                 ______________________________________                                        Yield (g)  4.1     4.5     4.5   7.3   15.8                                   Composition                                                                   of polymer                                                                    Functional group-                                                                        N-1-OH  N-1-OH  N-1-OH                                                                              N-0-OH                                                                              N-1-COOH                               containing monomer                                                            (A)                                                                           (% by mole)                                                                              73.3    15.8    51.8  0.5   0.9                                    Monomer (B)                                                                   (% by mole)                                                                   TFE        26.7    --      --    --    --                                     VdF        --      84.2    48.2  99.5  99.1                                   DSC measurement                                                               (° C.)                                                                 Tg         -1.1    -8.9    -8.1  --    --                                     Tm         --      --      --    171.7 172                                    Thermal decom-                                                                position temperature                                                          when weight                                                                   decreased by 1%                                                               (° C.)                                                                 Td         204.7   351     341   358   297                                    Molecular weight by                                                           GPC × 10.sup.4                                                          (THF type.sup.1),                                                             DMF type.sup.2))                                                              Mn         1.8.sup.1)                                                                            1.8.sup.1)                                                                            1.2.sup.1)                                                                          7.1.sup.2)                                                                          7.4.sup.2)                             Mw         3.0     2.9     2.4   12.4  14.8                                   IR analysis (cm.sup.-1)                                                       ν non-associated                                                                      3656    3645    3640  3622  3685 to 2800                           OH                                                                            ν associated OH                                                                       3466    3440    3425  3455                                         ν C═O                                                                             --      --      --    --    1770                                   ______________________________________                                    

EXAMPLE 19

Copolymerization ofperfluoro(1,1,6,6-tetrahydro-2-trifluoromethyl-3-oxa-5-hexenol) andtetrafluoroethylene/ethylene

A 500 mλ autoclave equipped with a valve, pressure gauge and thermometerwas charged with 1.4 g ofperfluoro(1,1,6,6-tetrahydro-2-trifluoromethyl-3-oxa-5hexenol) preparedin EXAMPLE 3, 100 g of 1,1,2-trichloro-1,2,2-trifluoroethane (R-113) and0.13 g of diisopropyl peroxydicarbonate (IPP) as shown in TABLE 3, andwas cooled with dry ice/methanol solution. Then the inside of the systemwas replaced by nitrogen sufficiently. Subsequently 30.3 g of a monomermixture prepared by pre-mixing tetrafluoroethylene and ethylene in amolar ratio of 80:20 in a bomb was fed through the valve to react at 45°C. for 1.5 hours with shaking.

With proceeding of the reaction, the gauge pressure before the reaction,i.e. 12.0 kgf/cm² G decreased to 7.5 kgf/cm² G. The un-reacted monomerwas discharged, and the precipitated white solids in the form of powderwere taken out, rinsed with water, cleaned with acetone and vacuum-driedto give 15.6 g of a copolymer.

The composition of the obtained copolymer was confirmed by ¹⁹ F-NMR andelementary analysis, and the presence of functional groups by infraredabsorption spectrum.

Also the melting point of the copolymer was measured by DSC, and theflow rate by a flow tester. The results are shown in TABLE 4.

EXAMPLES 20 TO 26

Copolymerization of the fluorine-containing monomer (A) with functionalgroup and the monomer mixture containing the fluorine-containing monomer(B)

The copolymers were prepared in the same manner as in EXAMPLE 19 exceptthat the composition of the fluorine-containing monomer (A) withfunctional group and the monomer mixture containing the monomer (B) (andcharged weights thereof), initiators and solvents (and charged weightsthereof) and reaction time were changed to the monomer (A), the monomermixture comprising the monomer (B) (and weights thereof), initiators andsolvents (and weights thereof) which are described in TABLE 3.

For EXAMPLES 20, 21 and 22, the copolymers after completion of thereaction were separated in the same manner as in EXAMPLE 19; for EXAMPLE23 in the same manner as in EXAMPLE 17; and for EXAMPLES 24, 25 and 26in the same manner as in EXAMPLE 14.

The composition, thermal analysis and flow rate or measurement ofmolecular weight by GPC of the copolymers prepared in EXAMPLES 20 to 26are shown in TABLE 4.

                                      TABLE 3                                     __________________________________________________________________________    Reaction conditions                                                                             Ex. 19                                                                            Ex. 20                                                                            Ex. 21                                                                            Ex. 22                                                                              Ex. 23                                                                            Ex. 24                                                                            Ex. 25                                                                            Ex. 26                        __________________________________________________________________________    Functional group-containing monomer (A)                                                         N-0-OH                                                                            N-1-OH                                                                            N-1-OH                                                                            N-1-COOH                                                                            N-1-OH                                                                            N-0-OH                                                                            N-1-OH                                                                            N-1-GE                        Charged amount (g)                                                                              1.4 2.1 2.1 2.2   1.54                                                                              1.64                                                                              1.84                                                                              2.86                          Monomer (B)                                                                   Composition of monomer mixture                                                (% by mole)                                                                   TFE               80  80  52  80    20  20  14  20                            VdF               --  --  --  --    80  60  74  60                            HFP               --  --  --  --    --  20  --  20                            CTFE              --  --  --  --    --  --  12  --                            E                 20  20  48  20    --  --  --  --                            Charged amount of monomer mixture (g)                                                           30.3                                                                              33.8                                                                              23.8                                                                              33.5  17.8                                                                              33.6                                                                              16.3                                                                              34.6                          Initiator         IPP IPP IPP IPP   IPP IPP IPP IPP                           Charged amount (g)                                                                              0.13                                                                              0.13                                                                              0.13                                                                              0.14  0.10                                                                              0.18                                                                              0.11                                                                              0.16                          Solvent           R-113                                                                             R-113                                                                             R-113                                                                             R-113 R-113                                                                             R-113                                                                             R-113                                                                             R-113                         Charged amount (g)                                                                              100 100 100 100   100 100 100 100                           Reaction temperature (° C.)                                                              45  45  45  45    45  45  45  45                            Reaction time (hr)                                                                              1.5 4.0 5.0 2.0   20  17  20  5.0                           __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Results of polymerization                                                                       Ex. 19                                                                             Ex. 20                                                                             Ex. 21                                                                             Ex. 22                                                                              Ex. 23                                                                            Ex. 24                                                                            Ex. 25                                                                            Ex. 26                     __________________________________________________________________________    Yield (g)         15.6 16.0 12.5 13.0  13.2                                                                              13.8                                                                              11.6                                                                              20.2                       Composition of polymer                                                        Functional group-containing monomer (A)                                                         N-0-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-COOH                                                                            N-1-OH                                                                            N-0-OH                                                                            N-1-OH                                                                            N-1-GE                     (% by mole)       2.4  1.8  2.5  3.7   0.4 0.3 2.4 7.0                        Monomer (B) (% by mole)                                                       TFE               67.4 72.5 49.0 62.3  19.8                                                                              25.7                                                                              14.2                                                                              24.0                       VdF               --   --   --   --    79.8                                                                              66.8                                                                              64.1                                                                              64.0                       HFP               --   --   --   --    --  7.2 --  5.0                        CTFE              --   --   --   --    --  --  19.3                                                                              --                         E                 30.2 25.7 48.5 34.0  --  --  --                             DSC measurement (° C.)                                                 Tg                --   --   --   --    --  --  -16 --                         Tm                235  252  258  223   133 109 --  94                         Thermal decomposition temperature                                             when weight decreased by 1% (° C.)                                     Td                350  384  366  272   374 359 367 283                        Molecular weight by GPC × 10.sup.4 (THF)                                Mn                --   --   --   --    7.5 7.1 7.6 6.5                        Mw                --   --   --   --    21.3                                                                              12.1                                                                              13.9                                                                              11.5                       Flow rate.sup.1) (ml/sec)                                                                       5.3 × 10.sup.-2                                                              4.1 × 10.sup.-2                                                              3.9 × 10.sup.-3                                                              3.2 × 10.sup.-2                                                               --  --  --  --                         IR analysis (cm.sup.-1)                                                       ν non-associated OH                                                                          3633 3633 3634 3680 to                                                                             3628                                                                              3624                                                                              3633                                                                              --                         ν associated OH                                                                              3478 3489 3481 2800  3442                                                                              3441                                                                              3456                                                                              --                         ν C═O      --   --   --   1716  --  --  --  --                         __________________________________________________________________________     .sup.1) Measured at 300° C. under 7 kg load                       

EXAMPLE 27

Copolymerization ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)and tetrafluoroethylene/ethylene monomer mixture

A one-liter stainless steel autoclave equipped with a stirrer, valve,pressure gauge and thermometer was charged with 250 mλ of pure water and0.16 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)prepared in EXAMPLE 6 as shown in TABLE 5, and the inside of the systemwas replaced sufficiently with nitrogen gas, and was evacuated. Then theautoclave was charged with 250 g of1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114) and 1.0 g of cyclohexane,and the inside of the system was kept at 35° C.

With stirring, the monomer mixture of tetrafluoroethylene/ethylene(molar ratio 82/18) prepared by pre-mixing in a bomb was fed underpressure to the autoclave so that the inside pressure thereof becomes8.0 kgf/cm² G. Subsequently 2.0 g of 50% methanol solution ofdi-n-propyl peroxydicarbonate was fed under pressure to initiate thereaction.

With proceeding of the polymerization, the pressure lowered, andtherefore at the time when reached 7.5 kgf/cm² G, the reaction pressurewas again raised to 8.0 kgf/cm² G with the monomer mixture comprisingtetrafluoroethylene/ethylene (molar ratio 52/48) which was separatelyprepared by mixing in a bomb. Then lowering and raising of the pressurewere repeated, and the monomer mixture of tetrafluoroethylene/ethylene(molar ratio 52/48) was fed.

Further with continuing feeding of the monomer mixture, every time whenabout 2.5 g of the monomer mixture was consumed after the initiation ofthe polymerization, 0.08 g of the above-mentioned fluorine-containingmonomer (N-1-OH) with hydroxyl group was fed under pressure nine times(0.72 g in total) to continue the polymerization. When the consumptionof the monomer mixture reached about 25 g, that is to say, after a timelapse of 1.5 hours from the initiation of the polymerization, thefeeding of the monomer mixture was stopped, the autoclave was cooled,and the un-reacted monomer and R-114 were discharged. White powder of25.6 g was obtained by treating in the same manner as in EXAMPLE 18.

The composition of the obtained copolymer was confirmed by ¹⁹ F-NMR andelementary analysis, and the presence of the functional groups byinfrared absorption spectrum.

Also the melting point of the copolymer was measured by DSC, and theflow rate by a flow tester. The results are shown in TABLE 6.

EXAMPLES 28 to 31

Copolymerization of the fluorine-containing monomer (A) with functionalgroup and tetrafluoroethylene/ethylene monomer mixture

Copolymers were prepared in the same manner as in EXAMPLE 27 except thatthe fluorine-containing monomer (A) and its charged amount, and theamounts of the monomer mixture comprising the monomer (B), initiator andcyclohexane were changed to those mentioned in TABLE 5.

The composition, thermal analysis and flow rate of the copolymersobtained in the respective EXAMPLES are shown in TABLE 6.

EXAMPLE 32

Copolymerization ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)and tetrafluoroethylene/ethylene monomer mixture

A copolymer was prepared in the same manner as in EXAMPLE 27 under theconditions shown in TABLE 5 except that a six-liter stainless steelautoclave equipped with a stirrer, valve, pressure gauge and thermometerwas used, and that there were used 1,500 mλ of pure water and 1,500 g of1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114) as a solvent. Thecomposition, thermal analysis and flow rate of the copolymer are shownin TABLE 6.

                                      TABLE 5                                     __________________________________________________________________________    Reaction conditions                                                                             Ex. 27                                                                             Ex. 28                                                                             Ex. 29                                                                             Ex. 30                                                                              Ex. 31                                                                              Ex. 32                           __________________________________________________________________________    Functional group-containing monomer (A)                                                         N-1-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-COOH                                                                            N-1-COOH                                                                            N-1-OH                           Initial charge (g)                                                                              0.16 0.16 0.3  0.16  0.31  1.89                             Additional charge (g)                                                                           0.08 × 9                                                                     0.08 × 9                                                                     0.15 × 9                                                                     0.08 × 9                                                                      0.16 × 9                                                                      0.94 × 9                                     times                                                                              times                                                                              times                                                                              times times times                            Monomer (B)                                                                   TFE/E molar ratio at initial charge                                                             82/18                                                                              82/18                                                                              82/18                                                                              82/18 82/18 82/18                            TFE/E molar ratio at additional charge                                                          52/48                                                                              52/48                                                                              52/48                                                                              52/48 52/48 52/48                            Initiator         NPP  NPP  NPP  NPP   NPP   NPP                              Charged amount (g)                                                                              1.0  1.0  1.0  1.0   1.0   6.0                              Cyclohexane (g)   1.0  1.6  1.6  1.0   1.6   9.6                              Reaction temperature (° C.)                                                              35   35   35   35    35    35                               Reaction time (hr)                                                                              1.5  1.2  1.4  1.5   2.0   1.6                              __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________    Results of polymerization                                                                       Ex. 27                                                                             Ex. 28                                                                             Ex. 29                                                                             Ex. 30                                                                              Ex. 31                                                                              Ex. 32                           __________________________________________________________________________    Yield (g)         25.6 22.2 27.5 33.0  50.5  222.8                            Composition of polymer                                                        Functional group-containing monomer (A)                                                         N-1-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-COOH                                                                            N-1-COOH                                                                            N-1-OH                           (% by mole)       0.2  0.2  0.4  0.2   0.5   0.4                              Monomer (B) (% by mole)                                                       TFE               56.3 54.9 54.9 55.0  55.2  56.8                             E                 43.5 44.9 44.7 44.8  44.3  42.8                             Melting point (° C.)                                                                     275  277  274  277   274   272                              Thermal decomposition temperature                                                               359  361  377  368   336   387                              when weight decreased by 1% (° C.)                                     Flow rate.sup.1) (ml/sec)                                                                       4.3 × 10.sup.-3                                                              2.7 × 10.sup.-2                                                              3.0 × 10.sup.-2                                                              4.0 × 10.sup.-3                                                               2.5 × 10.sup.-2                                                               3.1 × 10.sup.-1            IR analysis (cm.sup.-1)                                                       ν non-associated OH                                                                          3644 3644 3636 3680  3680  3645                             ν associated OH                                                                              3356 3350 3365 to 2800                                                                             to 2800                                                                             3360                             ν C═O      --   --   --   1789  1789  --                               __________________________________________________________________________     .sup.1) Measured at 300° C. under 7 kg load                       

EXAMPLE 33

Copolymerization ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol),tetrafluoroethylene and perfluoro(propyl vinyl ether)

A six-liter autoclave lined with glass and equipped with a stirrer,valve, pressure gauge and thermometer was charged with 1,500 mλ of purewater, followed by replacing with nitrogen gas sufficiently, and thenwas evacuated. Then 1,500 g of 1,1-dichloro-1,1,2,2tetrafluoroethane(R-114) was fed thereto. Afterwards as shown in TABLE 7, 2.4 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)prepared in EXAMPLE 6, 30 g of perfluoro(propyl vinyl ether) (PPVE) and210 g of methanol were fed under pressure by using nitrogen gas, and theinside of the system was kept at a temperature of 35° C.

With stirring, tetrafluoroethylene gas was fed under pressure so thatthe inside pressure becomes 8.0 kgf/cm² G. Subsequently 2.4 g of 50%methanol solution of di-n-propyl peroxydicarbonate was fed underpressure to initiate the reaction.

With proceeding of the polymerization, the pressure lowered, andtherefore at the time when decreased to 7.5 kgf/cm² G, the reactionpressure was raised to 8.0 kgf/cm² G again with tetrafluoroethylene gas,and lowering and raising of the pressure were repeated.

With continuing feeding of tetrafluoroethylene, after the initiation ofthe polymerization, every time when about 60 g of tetrafluoroethylenegas was consumed, 1.2 g of the above-mentioned fluorine-containingmonomer (N-1-OH) with hydroxyl group and 3.3 g of perfluoro(propyl vinylether) were fed under pressure 9 times respectively (N-1-OH totaling10.8 g, perfluoro(propyl vinyl ether) 29.7 g in total) to continue thepolymerization. At the time when about 600 g of tetrafluoroethylene wasconsumed from the initiation of the polymerization, that is, 5 to 6hours after, the feeding of tetrafluoroethylene was stopped and theautoclave was cooled. Then the un-reacted monomer and R-114 weredischarged.

White powder of 642 g was obtained by treating in the same manner as inEXAMPLE 18. The composition of the obtained copolymer was confirmed by¹⁹ F-NMR, and the presence of the functional groups by infraredabsorption spectrum.

Also the melting point of the copolymer was measured by DSC, and theflow rate by a flow tester.

The results are shown in Table 7.

EXAMPLES 34 AND 35

Copolymerization ofperfluoro(9,9-dihydro-2,5bistrifluoromethyl-3,6-dioxa-8-nonenol),tetrafluoroethylene and perfluoro(propyl vinyl ether)

Polymers were obtained in the same manner as in EXAMPLE 33 except thatthe charged amounts of the fluorine-containing monomer (N-1-OH) withhydroxyl group and perfluoro(propyl vinyl ether), and the amounts of aninitiator and methanol were changed to those mentioned in TABLE 7, andthen measurements were made in the same manner as in EXAMPLE 33.

The results are shown in TABLE 7.

                  TABLE 7                                                         ______________________________________                                        Conditions Results                                                                              Ex. 33   Ex. 34   Ex. 35                                    ______________________________________                                        Functional group-containing                                                                     N-1-OH   N-1-OH   N-1-OH                                    monomer (A)                                                                   Initial charge (g)                                                                              2.4      2.6      5.0                                       Additional charge (g)                                                                           1.2 × 9                                                                          3.6 × 9                                                                          3.7 × 9                                               times    times    times                                     Monomer B                                                                     Pressure for continuous                                                                         7.5-8.0  7.5-8.0  7.5-8.0                                   charging of TFE (kgf/cm.sup.2 G)                                              PPVE.sup.1) Initial charge (g)                                                                  30.0     48.6     50.3                                      PPVE Additional charge (g)                                                                      3.3 × 9                                                                          1.3 × 9                                                                          2.5 × 9                                               times    times    times                                     Initiator         NPP      NPP      NPP                                       Charged amount (g)                                                                              2.4      2.4      2.4                                       Methanol (g)      210      120      120                                       Reaction temperature (° C.)                                                              35       35       35                                        Reaction time (hr)                                                                              5.6      5.5      8.0                                       Yield (g)         642      671      652                                       Composition of polymer (% by mole)                                            Functional group-containing                                                                     0.4      0.6      1.0                                       monomer (A)                                                                   Monomer (B)                                                                   TFE               99.2     99.1     98.5                                      PPVE              0.4      0.3      0.5                                       Melting point (° C.)                                                                     311      309      308                                       Thermal decomposition temperature                                                               369      362      384                                       when weight decreased by 1% (° C.)                                     Flow rate (ml/sec).sup.2)                                                                       2.9 × 10.sup.-3                                                                  1.4 × 10.sup.-3                                                                  1.7 × 10.sup.-3                     IR analysis (cm.sup.-1)                                                       ν non-associated OH                                                                          3644     3651     3651                                      ν associated OH                                                                              3549     3549     3524                                      ______________________________________                                         .sup.1) PPVE: Perfluoro(propyl vinyl ether)                                   .sup.2) Measured at 372° C. under 7 kg load                       

EXAMPLE 36

Emulsion copolymerization ofperfluoro(1,1,9,9tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)and monomer mixture of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene

A one-liter autoclave made of glass and equipped with a stirrer, valve,pressure gauge and thermometer was charged with 500 mλ of pure water,1.0 g of ammonium perfluorooctanoate (PFOA) as an emulsifying agent and0.5 g ofperfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)prepared in EXAMPLE 6 as shown in TABLE 8, and, after the inside of thesystem was sufficiently replaced by nitrogen gas, the system was heatedto 60° C.

Subsequently, with stirring, the monomer mixture of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (molar ratio 60/20/20)which had been previously prepared by mixing in a bomb was fed underpressure so that the inside pressure became 8.0 kgf/cm² G at 60° C. Thenthe solution prepared by dissolving 0.5 g of ammonium persulfate (APS)in 5.0 mλ of pure water was fed under pressure with nitrogen gas toinitiate the reaction.

Since the pressure decreased with proceeding of the polymerization, atthe time when lowered to 7.5 kgf/cm² G, the reaction pressure was againraised to 8.0 kgf/cm² G by using the same VdF/TFE/HFP monomer mixture(molar ratio 60/20/20) as mentioned above. Thus lowering and raising ofthe pressure were repeated.

Further, with continuing feeding of the monomer mixture, every time whenabout 25 g of the monomer mixture was consumed after the initiation ofthe polymerization, 0.24 g of the above-mentioned fluorine-containingmonomer (N-1-OH) with hydroxyl group was fed under pressure 7 times(1.68 g in total) to continue the polymerization. At the time when about200 g of the monomer mixture was consumed from the initiation of thepolymerization, that is, 7.5 hours after, the above-mentioned autoclavewas cooled and the un-reacted monomer was discharged to give an aqueousemulsion.

This aqueous emulsion was freezed, and the resulting coagulate wasrinsed with water and dried to give 189 g of the rubber-like polymer.

The composition of the obtained copolymer was confirmed by ¹ H-NMR and¹⁹ F-NMR, and the presence of the functional groups by infraredabsorption spectrum.

Also the glass transition point (Tg) of the copolymer was measured byDSC, and the molecular weight by GPC analysis on the basis of the THFsolvent.

The results are shown in TABLE 9.

EXAMPLES 37 TO 42

Emulsion polymerization of a fluorine-containing monomer (A) withfunctional group and a monomer mixture mainly comprising vinylidenefluoride

Copolymers were prepared in the same manner as in EXAMPLE 36 except thatthe kind, initial charge, additional charge and the number of additionalcharges of the fluorine-containing monomer (A) with functional group,the composition of the monomer mixture comprising the monomer (B),initiator, emulsifying agent, reaction temperature and reaction timewere changed to the monomer (A), its initial charge, additional chargeand the number of additional charges, the monomer mixture of the monomer(B), initiator, emulsifying agent and the polymerization temperature andtime as shown in TABLE 8.

The results of measuring the composition of the copolymers obtained inEXAMPLES 37 to 42, thermal analysis and molecular weight by GPC areshown in TABLE 9.

                                      TABLE 8                                     __________________________________________________________________________    Reaction conditions                                                                             Ex. 36                                                                             Ex. 37                                                                             Ex. 38                                                                             Ex. 39                                                                             Ex. 40                                                                             Ex. 41                                                                              Ex. 42                       __________________________________________________________________________    Functional group-containing monomer (A)                                                         N-1-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-OH                                                                             N-1-COOH                                                                            N-1-COONH.sub.4              Initial charge (g)                                                                              0.50 2.15 1.13 4.98 4.89 2.20  2.5                          Additional charge (g)                                                                           0.24 × 7                                                                     0.60 × 5                                                                     0.60 × 5                                                                     1.65 × 5                                                                     --   1.15 × 5                                                                      --                                             times                                                                              times                                                                              times                                                                              times     times                              Monomer (B)                                                                   Composition of monomer mixture                                                (% by mole)                                                                   VdF               60   60   60   60   60   60    74                           TFE               20   20   20   20   20   20    14                           HFP               20   20   20   20   20   20    --                           CTFE              --   --   --   --   --   --    12                           Emulsifying agent PFOA PFOA PFOA PFOA PFOA PFOA  --                           Charged amount (g)                                                                              1.0  1.0  1.0  1.0  1.0  1.0   --                           Initiator         APS  APS  APS  APS  APS  APS   APS                          Charged amount (g)                                                                              0.5  0.5  0.5  0.5  0.5  0.5   0.2                          Reaction temperature (° C.)                                                              60   80   60   80   60   80    60                           Reaction time (hr)                                                                              7.5  5.8  9.1  11.0 4.5  4.8   2.5                          __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________    Results of polymerization                                                                       Ex. 36                                                                            Ex. 37                                                                            Ex. 38                                                                            Ex. 39                                                                            Ex. 40                                                                            Ex. 41                                                                              Ex. 42                            __________________________________________________________________________    Yield (g)         189 134 144 141 26.1                                                                              147   25.1                              Composition of polymer                                                        Functional group-containing monomer (A)                                                         N-1-OH                                                                            N-1-OH                                                                            N-1-OH                                                                            N-1-OH                                                                            N-1-OH                                                                            N-1-COOH                                                                            N-1-COONH.sub.4                   (% by mole)       0.1 0.5 0.4 1.3 2.5 0.4   0.7                               Monomer (B) (% by mole)                                                       VdF               62.8                                                                              63.0                                                                              62.4                                                                              63.1                                                                              66.3                                                                              63.5  72.2                              TFE               18.0                                                                              18.5                                                                              19.7                                                                              18.1                                                                              20.4                                                                              18.1  13.7                              HFP               19.1                                                                              18.0                                                                              17.5                                                                              17.5                                                                              10.8                                                                              18.0  --                                CTFE              --  --  --  --  --  --    13.4                              Measurement by DSC (° C.)                                              Tg                -17.0                                                                             -20.8                                                                             -47.0                                                                             -21.5                                                                             -23.0                                                                             -17.5 --                                Tm                --  --  --  --  --  --    80.6                              Thermal decomposition temperature                                             when weight decreased by 1% (° C.)                                     Td                380 405 369 395 395 353   356                               Molecular weight by GPC × 10.sup.4 (THF)                                Mn                21.4                                                                              7.1 21.6                                                                              5.1 6.5 9.2   28.5                              Mw                50.1                                                                              12.7                                                                              47.4                                                                              8.1 14.5                                                                              14.2  78.0                              IR analysis (cm.sup.-1) (cast film)                                           ν non-associated OH                                                                          --  --  --  --  --  3580 to                                                                             3490 to                           ν associated OH                                                                              3302                                                                              3300                                                                              3301                                                                              3301                                                                              3300                                                                              2650  2630(ν NH)                     ν C═O      --  --  --  --  --  1770  1669                              __________________________________________________________________________

EXAMPLE 43

Copolymerization ofperfluoro(9,9-dihydro-2,5bistrifluoromethyl-3,6-dioxa-8-nonenoic acid)and monomer mixture of tetrafluoroethylene/perfluoro(methyl vinyl ether)

A six-liter stainless steel autoclave equipped with a stirrer, valve,pressure gauge and thermometer was charged with 1,000 me of pure water,2.0 g ofperfluoro(9,9-dihydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenoic acid)(N-1-COOH) prepared in EXAMPLE 5 and 1.04 g of 1,4-diiodoperfluorobutane(ICF₂ CF₂ CF₂ CF₂ I), and was heated to 80° C. after the inside of thesystem was replaced by nitrogen gas sufficiently.

Subsequently, with stirring, the monomer mixture oftetrafluoroethylene/perfluoro(methyl vinyl ether) (PMVE) (molar ratio63/37) which had been previously prepared by mixing in a bomb, was fedunder pressure so that the inside pressure becomes 8.0 kgf/cm² G at 80°C. Then the solution prepared by dissolving 0.25 g of ammoniumpersulfate (APS) in 5.0 mλ of pure water was fed under pressure withnitrogen gas to initiate the reaction.

Since the pressure decreased with proceeding of the polymerization, atthe time when lowered to 7.5 kgf/cm² G, the reaction pressure was againraised to 8.0 kgf/cm² G by using the same TFE/PMVE (molar ratio 63/37)monomer mixture as mentioned above. Thus lowering and raising of thepressure were repeated.

At the time when about 200 g of the monomer mixture was consumed fromthe initiation of the polymerization, that is, 21 hours after, thefeeding of the monomer mixture was stopped, the above-mentionedautoclave was cooled and the un-reacted monomer was discharged to givean aqueous emulsion.

This aqueous emulsion was freezed, and the resulting coagulate wasrinsed with water and dried to give 198 g of the rubber-like polymer.

The composition of the obtained copolymer wasTFE/PMVE/N-1-COOH=59.8/39.8/0.4 (% by mole) by ¹ H-NMR and ¹⁹ F-NMRanalyses. At 1,780 cm⁻¹ of the infrared spectrum, the characteristicabsorption of --C═O was observed, and at 2,640 to 3,580 cm⁻¹, thecharacteristic absorptions of --OH were observed. The glass transitiontemperature (Tg) was -3.4° C., and the thermal decomposition temperatureTd when the weight decreased by 1% was 359° C. Mooney viscosity (100°C.) was ML₁₊₁₀ 60.

III. Examples of thermoplastic resin composition

For the following examples, the tests mentioned below were carried out.

(1) Tensile test

Measurements were made in accordance with ASTM D638 at a cross-headspeed of 10 mm/min at room temperature by using a type 5 dumbbell and aTENSILON universal tester available from Orientec Corporation.

(2) Bending test

Measurements were made in accordance with JIS K-6911 at a bending speedof 2 mm/min at room temperature by using a TENSILON universal testeravailable from Orientec Corporation.

(3) Izod impact test

Izod notched impact strength was measured in accordance with ASTM D256by using a U-F impact tester available from Ueshima Seisakusho Ltd.

(4) Deflection temperature under load

Measurements were made in accordance with JIS K7207 under N₂ gas flowunder a load of 18.5 kgf/cm² at the heat-up rate of 2° C./min by using aheat distortion tester available from Yasuda Seiki Seisakusho Ltd.

(5) Melt flow rate

Melt flow rate (g/10 min) was measured after preheating for 5 minutes byusing a 2 mm diameter and 8 mm long nozzle and a flow tester availablefrom Shimadzu Corporation.

(6) Hardness

Measurements were made in accordance with ASTM D2240 by using a type Adurometer.

(7) Shrinkage from mold dimensions

Shrinkage from mold dimensions in the flow direction and in thedirection at the right angle to the flow was measured in accordance withASTM D955.

(8) Coefficient of linear expansion

Coefficient of linear expansion was measured at a temperature rangingfrom 40° to 150° C. under a load of 0.16 kgf/cm² by using TMA availablefrom Rigaku Denki Co., Ltd.

REFERENCE EXAMPLE 5

Synthesis of a VdF/TFE/HFP copolymer without functional group

A vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymerwas obtained in the same manner as in EXAMPLE 36 except thatperfluoro(1,1,9,9tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol)was not used. At the time when 150 g of the monomer mixture ofvinylidene fluoride/tetrafluoroethylene/hexafluoropropylene (molar ratio60/20/20) was consumed (5.5 hours) in the polymerization reaction ofEXAMPLE 36, feeding thereof was stopped and the un-reacted monomer wasdischarged. The reaction product was then treated in the same manner asin EXAMPLE 36 to give 145 g of a rubber-like polymer.

The composition of the obtained polymer was vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene=61.3/18.9/19.8% by moleby using ¹⁹ F-NMR and ¹ H-NMR. The molecular weight by GPC analysis (THFsolvent) was 215,000 in number average molecular weight and 473,000 inweight average molecular weight. The glass transition point measured byDSC was -17° C., and the thermal decomposition temperature when theweight decreased by 1% was 420° C.

EXAMPLE 44

Improvement of mechanical strength by using a blend of polyphenylenesulfide resin and a fluorine-containing elastomer with functional group

A 60 cm³ Brabender mixer being set at 300° C. was charged with 44.8 g ofpoly(phenylene sulfide) resin (TOHPREN T4 available from Tohpren Co.,Ltd.). After melting at 50 rpm for four minutes, 15.1 g of thefluorine-containing elastomer with hydroxyl group obtained in EXAMPLE 38was added and kneading was carried out at 100 rpm for six minutes. Inthis case, as compared with COMPARATIVE EXAMPLE 1 as mentionedhereinafter, there was larger increase in torque at the time of mixing.The obtained composition was compression-molded at 300° C. to give testpieces. The bending test and Izod impact test were conducted by usingthe obtained test pieces. The results are shown in TABLE 10.

COMPARATIVE EXAMPLE 1

Kneading and molding were carried out in the same manner as in EXAMPLE44 except that the fluorine-containing elastomer without functionalgroup prepared in REFERENCE EXAMPLE 5 was used instead of thefluorine-containing elastomer with hydroxyl group obtained in EXAMPLE38, to give test pieces. The results are shown in TABLE 10.

COMPARATIVE EXAMPLE 2

Poly(phenyl sulfide) resin (same as in EXAMPLE 44) wascompression-molded at 300° C. to give test pieces. The tests werecarried out in the same manner as in EXAMPLE 44. The results are shownin TABLE 10.

                  TABLE 10                                                        ______________________________________                                        Test results    Ex. 44   Com. Ex. 1                                                                              Comp. Ex. 2                                ______________________________________                                        Composition (% by weight)                                                     Fluorine-containing polymer (D)                                                               20       --        --                                         with functional group                                                         EXAMPLE 38                                                                    Thermoplastic resin (E)                                                                       80       80        100                                        Poly(arylene sulfide)                                                         Other polymer (F)                                                                             --       20        --                                         REFERENCE EXAMPLE 5                                                           Properties of molded article                                                  Bending strength (kgf/cm.sup.2)                                                               780      570       1150                                       Bending modulus (kgf/cm.sup.2)                                                                38700    35000     37000                                      Izod impact strength                                                                            3.4      1.4       1.3                                      (kgf · cm/cm)                                                        ______________________________________                                    

As it is clear from the results in TABLE 10, as compared with the blend(COMPARATIVE EXAMPLE 1) of the fluorine-containing elastomer withoutfunctional group, it is possible to improve Izod impact strength moreeffectively without remarkably lowering mechanical properties, byblending the hydroxyl-introduced fluorine-containing elastomer with thepoly(phenylene sulfide) resin (EXAMPLE 44).

EXAMPLE 45

Blend of a polyamide resin and a fluorine-containing elastomer withfunctional group

A 60 cm³ Brabender mixer being set at 190° C. was charged with 22.5 g ofpolyamide 12 (UBE NYLON 12 3024B available from Ube Industries, Ltd.),and after melting at 10 rpm for 2 minutes, 33.8 g of thefluorine-containing elastomer with carboxyl group obtained in EXAMPLE 41was added at 50 rpm, followed by kneading at 100 rpm for 5 minutes. Theobtained composition was compression-molded at 200° C. to give testpieces. The results are shown in TABLE 11.

EXAMPLE 46

Enhancement of chemical resistance by blending a polyamide resin and afluorine-containing elastomer with functional group

Kneading and molding were carried out in the same manner as in EXAMPLE45 except that 33.2 g of polyamide 12 (same as in EXAMPLE 45) and 14.2 gof the fluorine-containing elastomer with carboxyl group prepared inEXAMPLE 41 were used, to give test pieces.

The tensile test and chemical resistance test were carried out by usingthe obtained test pieces.

(Chemical resistance test)

The test piece was dipped in a toluene/isooctane/methanol=40/40/20 (% byvolume) mixed solvent at 50° C. for 72 hours and then the volume changeand strength retention were measured in accordance with JIS-K630.

The results are shown in TABLE 11.

EXAMPLE 47

Addition of a fluorine-containing polymer with functional group to ablend of a polyamide resin and PVDF

A 60 cm³ blender mixer being set at 210° C. was charged with 32.7 g ofpolyamide 12 (same as in EXAMPLE 45), and after melting at 10 rpm for 2minutes, 11.7 g of PVDF (NEOFLON VDF VP-800 available from DaikinIndustries, Ltd.) was added. Then after mixing for 2 minutes, 2.3 g of afluorine-containing polymer with carboxyl group of EXAMPLE 18 was addedat 50 rpm, followed by kneading at 100 rpm for 5 minutes. The obtainedcomposition was compression-molded at 210° C. to give test pieces. Theresults are shown in TABLE 11.

EXAMPLE 48

Addition of a fluorine-containing polymer with functional group to ablend of a polyamide resin and PVdF

Kneading and molding were carried out in the same manner as in EXAMPLE47 except that 9.3 g of PVDF (same as in EXAMPLE 47) and 4.7 g of afluorine-containing polymer with carboxyl group of EXAMPLE 18 were used,to give test pieces. The results are shown in TABLE 11.

EXAMPLE 49

Addition of a fluorine-containing polymer with functional group to ablend of a polyamide resin and PVDF

Kneading and molding were carried out in the same manner as in EXAMPLE47 except that the fluorine-containing polymer having glycidyl groupobtained in EXAMPLE 26 was used instead of the fluorine-containingpolymer with carboxyl group obtained in EXAMPLE 18, to give test pieces.

EXAMPLE 50

Addition of a fluorine-containing polymer with functional group to ablend of a polyamide resin and ETFE

A 60 cm³ blender mixer being set at 240° C. was charged with 33.0 g ofpolyamide 12 (same as in EXAMPLE 45), and after melting at 10 rpm for 2minutes, 11.8 g of ETFE (NEOFLON ETFE EP-610 available from DaikinIndustries, Ltd.) was added. Then after mixing for two minutes, 2.4 g ofthe fluorine-containing polymer with carboxyl group prepared in EXAMPLE22 was added at 50 rpm, followed by kneading at 100 rpm for 5 minutes.

The obtained composition was compression-molded at 240° C. to give testpieces. The results are shown in TABLE 11.

EXAMPLE 51

Addition of a fluorine-containing polymer with functional group to ablend of a polyamide resin and ETFE

Kneading and molding were carried out in the same manner as in EXAMPLE50 except that 9.4 g of ETFE (same as in EXAMPLE 50) and 4.8 g of thefluorine-containing polymer with carboxyl group obtained in EXAMPLE 22were used, to give test pieces. The results are shown in TABLE 11.

                                      TABLE 11                                    __________________________________________________________________________    Test results  Ex. 45                                                                            Ex. 46                                                                            Ex. 47                                                                            Ex. 48                                                                            Ex. 49                                                                            Ex. 50                                                                            Ex. 51                                  __________________________________________________________________________    Composition (% by weight)                                                     Fluorine-containing polymer (D)                                               with functional group                                                         Polymer of EXAMPLE 18                                                                       --  --  5   10  --  --  --                                      Polymer of EXAMPLE 22                                                                       --  --  --  --  --  5   10                                      Polymer of EXAMPLE 26                                                                       --  --  --  --  5   --  --                                      Polymer of EXAMPLE 41                                                                       60  30  --  --  --  --  --                                      Thermoplastic resin (E)                                                       Polyamide 12  40  70  70  70  70  70  70                                      Fluorine-containing polymer (F)                                               without functional group                                                      PVdF.sup.1)   --  --  25  20  25  --  --                                      ETFE.sup.2)   --  --  --  --  --  25  20                                      Properties of molded article                                                  (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                             166 376 460 430 458 390 360                                     Tensile modulus (kgf/cm.sup.2)                                                              3900                                                                              7600                                                                              10700                                                                             12900                                                                             9900                                                                              10400                                                                             11900                                   (Chemical resistance test)                                                    Volume change (%)                                                                           --  15.7                                                                              10.4                                                                              11.3                                                                              12.8                                                                              10.9                                                                              10.4                                    Strength retention.sup.3) (%)                                                               --  102 102 97  88  85  80                                      __________________________________________________________________________     .sup.1) NEOFLON VDF VP800 available from Daikin Industries, Ltd.              .sup.2) NEOFLON ETFE EP610 available from Daikin Industries, Ltd.             .sup.3) [(Tensile strength after chemical resistance test)/(tensile           strength before test)] × 100                                       

COMPARATIVE EXAMPLE 3

Kneading and molding were carried out in the same manner as in EXAMPLE45 except that a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene copolymer withoutfunctional group (DAI-EL G-902 available from Daikin Industries, Ltd.)was used instead of the fluorine-containing polymer with carboxyl groupobtained in EXAMPLE 41, to give test pieces. The results are shown inTABLE 12.

COMPARATIVE EXAMPLE 4

Kneading and molding were carried out in the same manner as in EXAMPLE46 except that the fluorine-containing elastomer without functionalgroup (same as in COMPARATIVE EXAMPLE 3) was used instead of thefluorine-containing elastomer with carboxyl group, which was prepared inEXAMPLE 41, to give test pieces. The results are shown in TABLE 12.

COMPARATIVE EXAMPLE 5

A blender mixer being set at 210° C. was charged with 32.7 g ofpolyamide 12 (same as in EXAMPLE 45), and after melting at 10 rpm for 2minutes, 14.0 g of PVdF (same as in EXAMPLE 47) was added, followed bykneading at 100 rpm for 5 minutes. Test pieces were prepared in the samemanner as in EXAMPLE 47. The results are shown in TABLE 12.

COMPARATIVE EXAMPLE 6

A blender mixer being set at 240° C. was charged with 33.0 g ofpolyamide 12 (same as in EXAMPLE 45), and after melting at 10 rpm for 2minutes, 14.2 g of ETFE (same as in EXAMPLE 50) was added, followed bykneading at 100 rpm for 5 minutes. Test pieces were prepared in the samemanner as in EXAMPLE 50. The results are shown in TABLE 12.

COMPARATIVE EXAMPLE 7

Test pieces were prepared by kneading and molding in the same manner asin EXAMPLE 47 except that epoxy-modified polystyrene-acrylic graftpolymer type compatibilizing agent (REZEDA GP300 available from ToagoseiChemical Industry Co., Ltd.) was used instead of the fluorine-containingpolymer with carboxyl group, which was prepared in EXAMPLE 18. Theresults are shown in TABLE 12

COMPARATIVE EXAMPLE 8

Polyamide 12 (same as in EXAMPLE 45) was compression-molded at 190C togive test pieces. The results are shown in TABLE 12.

                                      TABLE 12                                    __________________________________________________________________________    Test results  Com. Ex. 3                                                                          Com. Ex. 4                                                                          Com. Ex. 5                                                                          Com. Ex. 6                                                                          Com. Ex. 7                                                                          Com. Ex. 8                        __________________________________________________________________________    Composition (% by weight)                                                     Thermoplastic resin (D)                                                       Polyamide 12  40    70    70    70    70    100                               Fluorine-containing polymer (F)                                               without functional group                                                      VdF/TFE/HFP copolymer                                                                       60    30    --    --    --    --                                (fluorine-containing elastomer).sup.1)                                        PVdF.sup.2)   --    --    30    --    25    --                                ETFE.sup.3)   --    --    --    30    --    --                                Other acryl type                                                              compatibilizing agent.sup.4)                                                                --    --    --    --    5     --                                Properties of molded article                                                  (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                             32    287   453   350   471   416                               Tensile modulus (kgf/cm.sup.2)                                                              640   6600  9600  9400  9300  8000                              (Chemical resistance test)                                                    Volume change (%)                                                                           --    15.8  11.5  14    28    15.8                              Strength retention.sup.5) (%)                                                               --    70    57.2  48.3  53    74                                __________________________________________________________________________     .sup.1) DMEL G902 available from Daikin Industries, Ltd.                      .sup.2) NEOFLON VDF VP800 available from Daikin Industries, Ltd.              .sup.3) NEOFLON ETFE EP610 available from Daikin Industries, Ltd.             .sup.4) RESEDA GP300 available from Toagosei Chemical Industry Co., Ltd.      .sup.5) [(Tensile strength after chemical resistance test)/(tensile           strength before test)] × 100                                       

As it is clear from a comparison between the tensile test results ofEXAMPLE 45 (TABLE 11) and COMPARATIVE EXAMPLE 3 (TABLE 12), the tensilestrength and tensile modulus can be considerably enhanced by introducinga carboxyl group to the fluorine-containing polymer in blending withpolyamide.

As it is clear from the respective test results of EXAMPLES 46 to 51 inTABLE 11, excellent mechanical properties and chemical resistance areobtained by blending the fluorine-containing polymer with carboxyl groupor the fluorine-containing polymer with glycidyl group with thepolyamide resin.

Particularly in case of the blend of the fluorine-containing polymerwithout functional group with polyamide (COMPARATIVE EXAMPLES 4 to 6 inTABLE 12), tensile strength lowers remarkably after the chemicalresistance test, and also in case of a blend (COMPARATIVE EXAMPLE 7) inwhich the epoxy-modified polystyrene-acrylic graft polymer typecompatibilizing agent was added, though enhancement of tensile strengthcould be initially observed, the strength lowered remarkably after thechemical resistance test.

On the contrary, in case of the blend of the fluorine-containing polymerwith carboxyl group or glycidyl group with polyamide, not only anexcellent mechanical properties but also excellent tensile strengthafter the chemical resistance test were exhibited. That is, it was foundthat there can be obtained a composition having the enhanceddispersibility and surface adhesivity of the fluorine-containing polymerin the blend with polyamide by introducing a functional group to thefluorine-containing polymer.

EXAMPLE 52

Blend of a liquid crystal polyester and the fluorine-containingelastomer with hydroxyl group

A 60 cm³ Brabender mixer being set at 200° C. was charged with 26.0 g ofa liquid crystal polyester (NOVACCURATE E310 available from MitsubishiChemical Corp.), and after melting at 10 rpm for 1.5 minutes, 38.9 g ofthe fluorine-containing elastomer with hydroxyl group prepared inEXAMPLE 36 was added at 50 rpm, followed by kneading at 100 rpm for 5minutes. The obtained composition was compression-molded at 200° C. togive test pieces. The tensile test was carried out by using the testpieces. The results are shown in TABLE 13.

EXAMPLE 53

Blend of a liquid crystal polyester and the fluorine-containingelastomer with hydroxyl group

Kneading and molding were carried out in the same manner as in EXAMPLE52 except that the fluorine-containing elastomer with hydroxyl groupprepared in EXAMPLE 37 was used, to give test pieces. The results areshown in TABLE 13.

EXAMPLES 54 AND 55

Blend of a liquid crystal polyester and the fluorine-containingelastomer with hydroxyl group

Kneading and molding were carried out in the same manner as in EXAMPLE52 except that 41.1 g of a liquid crystal polyester (same as in EXAMPLE52) and 17.6 g of the fluorine-containing elastomer with hydroxyl groupobtained in EXAMPLE 36 (EXAMPLE 54) or EXAMPLE 37 (EXAMPLE 55),respectively, were used, to give test pieces. The results are shown inTABLE 13.

EXAMPLE 56

Blend of a liquid crystal polyester and the fluorine-containingelastomer with hydroxyl group

Kneading and molding were carried out in the same manner as in EXAMPLE54 except that kneading and compression-molding were conducted at 300°C. by using 42.5 g of the liquid crystal polyester (VECTRA A950available from Polyplastics Co., Ltd.) and 18.2 g of thefluorine-containing elastomer with hydroxyl group prepared in EXAMPLE36, to give test pieces. The results are shown in TABLE 13.

COMPARATIVE EXAMPLES 9 TO 11

With the use of a fluorine-containing elastomer without functional group(same as in COMPARATIVE EXAMPLE 3) instead of the fluorine-containingelastomer with hydroxyl group, kneading and molding were carried out inthe same manner as in EXAMPLE 52 for COMPARATIVE EXAMPLE 9, in EXAMPLE54 for COMPARATIVE EXAMPLE 10 and in EXAMPLE 56 for COMPARATIVE EXAMPLE11, respectively, to give test pieces. The results are shown in TABLE13.

Also the molded articles obtained in EXAMPLES 55 and 56 and COMPARATIVEEXAMPLES 10 and 11 were frozen in liquid nitrogen and broken, and thebroken surfaces were observed with a scanning type electron microscope.The photographs (×500) of those cut surfaces are shown in FIGS. 2, 3, 4and 5, respectively.

                                      TABLE 13                                    __________________________________________________________________________                                      Com.                                                                              Com.                                                                              Com.                                Test results  Ex. 52                                                                            Ex. 53                                                                            Ex. 54                                                                            Ex. 55                                                                            Ex. 56                                                                            Ex. 9                                                                             Ex. 10                                                                            Ex. 11                              __________________________________________________________________________    Composition (% by weight)                                                     Fluorine-containing polymer (D)                                               with functional group                                                         Polymer of EXAMPLE 36                                                                       60  --  30  --  30  --  --  --                                  Polymer of EXAMPLE 37                                                                       --  60  --  30  --  --  --  --                                  Thermoplastic resin (E)                                                       Liquid crystal polyester (1).sup.1)                                                         40  40  70  70  --  40  70  --                                  Liquid crystal polyester (II).sup.2)                                                        --  --  --  --  70  --  --  70                                  Fluorine-containing polymer (F)                                               without functional group                                                      VdF/TFE/HFP copolymer.sup.3)                                                                --  --  --  --  --  60  30  30                                  (elastomer)                                                                   Properties of composition                                                     (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                             115 151 360 333 692 22.9                                                                              215 560                                 Tensile modulus (kgf/cm.sup.2)                                                              4100                                                                              3400                                                                              15000                                                                             12700                                                                             23100                                                                             480 9800                                                                              17900                               Electron microscope photograph                                                              --  --  --  FIG. 2                                                                            FIG. 3                                                                            --  FIG. 4                                                                            FIG. 5                              of cut surface                                                                __________________________________________________________________________     .sup.1) NOVACCURATE E310 available from Mitsubishi Chemical Corp.             .sup.2) VECTRA A950 available from Polyplastics Co., Ltd.                     .sup.3) DMEL G902 available from Daikin Industries. Ltd.                 

As it is clear from the results of TABLE 13, mechanical properties(tensile strength tensile modulus) can be considerably enhanced byblending the hydroxyl-introduced fluorine-containing elastomer with theliquid crystal polyester (EXAMPLES 52 to 56) as compared with the casewhere the conventional fluorine-containing elastomer is blended(COMPARATIVE EXAMPLES 9 to 11).

Also as it is clear from comparing the photographs of the cut surfacesbetween FIG. 2 with FIG. 4 and FIG. 3 with FIG. 5, it can be recognizedthat in the molded articles prepared by using the hydroxyl-containingelastomer (FIG. 2 and FIG. 3), the liquid crystal polyester formedmatrix and the fluorine-containing elastomer was finely dispersedtherein.

It is assumed that by introducing hydroxyl group into thefluorine-containing polymer, the hydroxyl group reacts partly with theliquid crystal polyester to enhance dispersibility with each other, andas a result, increase mechanical properties more effectively.

EXAMPLE 57

Addition of the fluorine-containing polymer with functional group to theblend of a liquid crystal polyester and PVDF

A 60 cm³ Brabender mixer being set at 20 ° C. was charged with 21.7 g ofa liquid crystal polyester (same as in EXAMPLE 52), and after melting at10 rpm for 1.5 minutes, 38.3 g of PVDF (same as in EXAMPLE 47) wasadded, followed by mixing for 2 minutes. Then 3.8 g of thefluorine-containing polymer with hydroxyl group prepared in EXAMPLE 17was added at 50 rpm, followed by kneading at 100 rpm for 5 minutes. Theobtained composition was crushed and then molded by an injection moldingmachine at a cylinder temperature of 200° to 250° C. and a dietemperature of 80° C. to give test pieces. The measurement of tensiletest, bending test and melt flow rate were conducted by using theobtained test pieces. The results are shown in TABLE 14.

EXAMPLE 58

Addition of a fluorine-containing polymer with functional group to ablend of a liquid crystal polyester and PVdF

Kneading and molding were carried out in the same manner as in EXAMPLE57 except that 24.5 g of a liquid crystal polyester (same as in EXAMPLE52), 43.2 g of PVdF (same as in EXAMPLE 47) and 4.4 g of thefluorine-containing polymer having hydroxyl group, which was obtained inEXAMPLE 37, were used, to give test pieces.

The results are shown in TABLE 14.

COMPARATIVE EXAMPLE 12

Kneading and molding were carried out in the same manner as in EXAMPLE57 except that a VdF/TFE/HFP copolymer (same as in COMPARATIVE EXAMPLE3) without functional group was used instead of the fluorine-containingpolymer with hydroxyl group prepared in EXAMPLE 17, to give test pieces.The results are shown in EXAMPLE 14.

COMPARATIVE EXAMPLE 13

A blender mixer being set at 200° C. was charged with 24.4 g of a liquidcrystal polyester (same as in EXAMPLE 52), and after melting at 10 rpmfor 1.5 minutes, 47.4 g of PVDF (same as in EXAMPLE 47) was added at 50rpm, followed by kneading at 100 rpm. The obtained composition wasmolded in the same manner as in EXAMPLE 57 to give test pieces. Theresults are shown in TABLE 14.

                  TABLE 14                                                        ______________________________________                                                                       Com.   Com.                                    Test Results Ex. 57   Ex. 58   Ex. 12 Ex. 13                                  ______________________________________                                        Composition                                                                   (% by weight)                                                                 Fluorine-containing                                                           polymer (D) with                                                              functional group                                                              Polymer of    5       --       --     --                                      EXAMPLE 17                                                                    Polymer of   --        5       --     --                                      EXAMPLE 37                                                                    Thermoplastic resin (E)                                                                    35       35       35     35                                      Liquid crystal                                                                polyester (I).sup.1)                                                          Fluorine-containing                                                           polymer (F) without                                                           functional group                                                              PVdF.sup.2)  60       60       60     65                                      VdF/TFE/HFP  --       --        5     --                                      copolymer.sup.3)                                                              (elastomer)                                                                   Properties of composition                                                     (Tensile test)                                                                Tensile strength                                                                           735      675      642    720                                     (kgf/cm.sup.2)                                                                Tensile modulus                                                                            30400    30200    29000  28400                                   (kgf/cm.sup.2)                                                                (Bending test)                                                                Bending strength                                                                           770      741      476    573                                     (kgf/cm.sup.2)                                                                Bending Modulus                                                                            27500    27500    24300  27300                                   (kgf/cm.sup.2)                                                                Melt flow rate.sup.4)                                                                        46.2     52.5     65.6   65.8                                  (g/10 min)                                                                    ______________________________________                                         .sup.1) NOVACCURATE E310 available from Mitsubishi Chemical Corp.             .sup.2) NEOFLON VDF VP800 available from Daikin Industries, Ltd.              .sup.3) DAIEL G902 available from Daikin Industries, Ltd.                     .sup.4) At 250° C. under 5 kgf/cm.sup.2 load                      

As is clear from TABLE 14, tensile modulus, bending characteristics andmoldability were enhanced by adding the fluorine-containing polymer withhydroxyl group at the time when blending the liquid crystal polyesterand PVDF.

Even in case of a simple blending of the liquid crystal polyester andPVdF, it is possible to improve particularly tensile strength of PVdFsince the liquid crystal polyester is oriented in the injection moldingdirection. However since dispersibility and surface adhesivity areinsufficient, characteristics in the direction of the right angle to theorientation, that is, bending characteristics becomes insufficient.Contrarily in case where the fluorine-containing polymer with functionalgroup is added when blending the liquid crystal polyester and PVdF,dispersibility and surface adhesivity can be improved and tensilemodulus and bending characteristics can be enhanced more.

EXAMPLES 59 AND 60

Addition of the fluorine-containing polymer with functional group whenblending PVdF and the liquid crystal polyester (II)

PVdF (same as in EXAMPLE 47), the liquid crystal polyester (same as inEXAMPLE 56) and the fluorine-containing polymer with hydroxyl groupprepared in EXAMPLE 38 were blended homogeneously in the amounts shownin TABLE 15, and then kneaded and extruded at 280° to 300° C. by abiaxial extrusion machine to give pellets. Test pieces were prepared byusing these pellets by an injection molding machine at a cylindertemperature of 240° to 290° C. and a die temperature of 50° C., and thentensile test, bending test and measurement of a deflection temperatureunder load were carried out. The results are shown in TABLE 15.

COMPARATIVE EXAMPLE 14

PVDF (same as in EXAMPLE 47), the liquid crystal polyester (same as inEXAMPLE 56) and the VdF/TFE/HFP copolymer (same as in COMPARATIVEEXAMPLE 3) were homogeneously blended in the amounts shown in TABLE 15,kneaded by an extrusion machine and injection-molded in the same manneras in EXAMPLE 59 to give test pieces. The results are shown in TABLE 15.

COMPARATIVE EXAMPLE 15

PVdF (same as in EXAMPLE 47) and the liquid crystal polyester (EXAMPLE56) were kneaded and molded in the same manner as in EXAMPLE 59 to givetest pieces. The results are shown in TABLE 15.

COMPARATIVE EXAMPLE 16

PVdF pellets (same as in EXAMPLE 47) were injection-molded in the samemanner as in EXAMPLE 59 to give test pieces. The results are shown inTABLE 15.

                                      TABLE 15                                    __________________________________________________________________________                            Com. Com. Com.                                        Test Results  Ex. 59                                                                             Ex. 60                                                                             Ex. 14                                                                             Ex. 15                                                                             Ex. 16                                      __________________________________________________________________________    Composition (% by weight)                                                     Fluorine-containing polymer (D)                                                              3    6   --   --   --                                          with functional group                                                         Polymer of EXAMPLE 38                                                         Thermoplastic resin (E)                                                                     20   20   20   20   --                                          Liquid crystal                                                                polyester (II).sup.1)                                                         Fluorine-containing polymer (F)                                               without functional group                                                      PVdF.sup.2)   77   74   77   80   100                                         VdF/TFE/HFP copolymer.sup.3)                                                                --   --    3   --   --                                          (elastomer)                                                                   Properties of composition                                                     (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                             745  766  710  790  720                                         Tensile modulus (kgf/cm.sup.2)                                                              27200                                                                              27900                                                                              25900                                                                              26400                                                                              11400                                       (Bending test)                                                                Bending strength (kgf/cm.sup.2)                                                             770  740  760  780  680                                         Bending modulus (kgf/cm.sup.2)                                                              39300                                                                              38300                                                                              37700                                                                              38500                                                                              13700                                       Deflection temperature under                                                                 150.0                                                                              150.4                                                                              140.7                                                                              130.8                                                                              108.0                                      load (° C.)                                                            Melt flow rate.sup.4) (g/10 min)                                                            117  125  108  104    45.2                                                                            (35.1).sup.5)                           __________________________________________________________________________     .sup.1) VECTRA A950 available from POLYPLASTICS CO., LTD.                     .sup.2) NEOFLON VDF VP800 available from Daikin Industries, Ltd.              .sup.3) DAIEL G902 available from Daikin Industries, Ltd.                     .sup.4) At 300° C. under 5 kgf/cm.sup.2 load                           .sup.5) Value in the parenthesis is one measured at 250° C. under      kgf/cm.sup.2 load                                                        

The results of TABLE 15 indicate that injection-molded articles whichare prepared by adding the fluorine-containing polymer with hydroxylgroup when PVdF and the liquid crystal polyester are kneaded andextruded, can be endowed with a deflection temperature under load andmoldability of PVdF which are improved more effectively as compared withthe simple blend of PVdF and the liquid crystal polyester.

EXAMPLE 61 AND COMPARATIVE EXAMPLES 17 and 18

Addition of the fluorine-containing polymer with functional group at thetime when blending ETFE and the liquid crystal polyester (III)

ETFE (NEOFLON ETFE EP-521 available from Daikin Industries, Ltd.), theliquid crystal polyester (SUMIKA SUPER LCP E7000 available from SumitomoChemical Co., Ltd.) and the fluorine-containing polymer with hydroxylgroup prepared in EXAMPLE 32 were homogeneously blended in the amountsshown in TABLE 16 by a rocking mixer, and then kneaded and extruded at280° to 300° C. by a biaxial extrusion machine to give pellets. Testpieces were then prepared by using the pellets with an injection moldingmachine at a cylinder temperature of 280° to 320° C. and a dietemperature of 100° C. The tensile test, bending test and measurementsof shrinkage from mold dimensions, a coefficient of linear expansion anda deflection temperature under load were conducted. The results areshown in TABLE 16.

                  TABLE 16                                                        ______________________________________                                                                   Com.     Com.                                      Test Results      Ex. 61   Ex. 17   Ex. 18                                    ______________________________________                                        Composition (% by weight)                                                     Fluorine-containing polymer (D)                                                                  5       --       --                                        with functional group                                                         Polymer of EXAMPLE 32                                                         Thermoplastic resin (E)                                                                         20       20       --                                        Liquid crystal                                                                polyester (III).sup.1)                                                        Fluorine containing polymer (F)                                                                 75       80       100                                       without functional group                                                      ETFE.sup.2)                                                                   Properties of composition                                                     (Shrinkage from mold dimensions)                                              Flow direction (%)                                                                                 0.07     0.15     1.95                                   Direction vertical to flow (%)                                                                     3.60     3.74     3.91                                   (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                                 360      320      360                                       Tensile modulus (kgf/cm.sup.2)                                                                  20500    18000    6300                                      (Bending test)                                                                Bending strength (kgf/cm.sup.2)                                                                 485      472      --                                        Bending modulus (kgf/cm.sup.2)                                                                  31400    29600    --                                        Coefficient of linear expansion.sup.3)                                                            3.2       3.70     7.14                                   (× 10.sup.5 /° C.                                                Deflection temperature under load                                                               118      105        82.2                                    (° C.)                                                                 ______________________________________                                         .sup.1) SUMIKA SUPER LCP E7000 available from Sumitomo Chemical Co., Ltd.     .sup.2) NEOFLON ETFE EP521 available from Daikin Industries, Ltd.             .sup.3) At 40° to 150° C.                                  

EXAMPLES 62 TO 64 AND COMPARATIVE EXAMPLES 19 and 20

Addition of the fluorine-containing polymer with functional group at thetime when blending PFA and the liquid crystal polyester (IV)

PFA (NEOFLON PFA AP-201 available from Daikin Industries, Ltd.), theliquid crystal polyester (SUMIKA SUPER LCP E6000 available from SumitomoChemical Co., Ltd.) and the fluorine-containing polymer with hydroxylgroup prepared in EXAMPLE 34 or 35 were homogeneously blended in theamounts shown in TABLE 17 by a rocking mixer, and then kneaded andextruded at 350° to 370° C. by a biaxial extrusion machine to givepellets. Test pieces were then prepared by using the pellets with aninjection molding machine at a cylinder temperature of 3400 to 360° C.and a die temperature of 190° C., and the same measurements as inEXAMPLE 61 were conducted. The results are shown in TABLE 17.

                                      TABLE 17                                    __________________________________________________________________________                                  Com. Com.                                       Test Results   Ex. 62                                                                             Ex. 63                                                                             Ex. 64                                                                             Ex. 19                                                                             Ex. 20                                     __________________________________________________________________________    Composition (% by weight)                                                     Fluorine-containing polymer (D)                                               with functional group                                                         Polymer of EXAMPLE 34                                                                        --   --   10   --   --                                         Polymer of EXAMPLE 35                                                                        2    5    --   --   --                                         Thermoplastic resin (E)                                                                      30   30   30   30   --                                         Liquid crystal                                                                polyester (IV).sup.1)                                                         Fluorine-containing polymer (F)                                                              68   65   60   70   100                                        without functional group                                                      PFA.sup.2)                                                                    Properties of composition                                                     (Shrinkage from mold dimension)                                               Flow direction (%)                                                                           -0.37                                                                              -0.38                                                                              -0.38                                                                              -0.34                                                                              4.3                                        Direction vertical to flow (%)                                                               4.2  4.0  3.4  4.3  4.0                                        (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                              535  506  485  470  181                                        Tensile modulus (kgf/cm.sup.2)                                                               29200                                                                              30600                                                                              28600                                                                              25200                                                                              4100                                       (Bending test)                                                                Bending strength (kgf/cm.sup.2)                                                              503  480  478  465  193                                        Bending modulus (kgf/cm.sup.2)                                                               49800                                                                              47600                                                                              47600                                                                              43000                                                                              5600                                       Coefficient of linear                                                                        2.36 2.26 2.21 2.63 8.91                                       expansion (× 10.sup.5 /° C.).sup.3)                              Deflection temperature under load                                                            247  249  251  235  64                                         (° C.)                                                                 __________________________________________________________________________     .sup.1) SUMIKA SUPER LCP E6000 available from Sumitomo Chemical Co., Ltd.     .sup.2) NEOFLON PFA AP201 available from Daikin Industries, Ltd.              .sup.3) At 40° to 150° C.                                  

The results of TABLES 16 and 17 indicate that mechanical properties anddimensional stability of molded articles can be improved, particularly acoefficient of linear expansion and a deflection temperature under loadcan be improved more effectively by adding the fluorine-containingpolymer with hydroxyl group when blending ETFE or PFA and the liquidcrystal polyester.

EXAMPLE 65

A thermoplastic elastomer composition prepared by melt-blending thefluorine-containing elastomer with hydroxyl group and the liquid crystalpolyester

Kneading and molding were carried out in the same manner as in EXAMPLE52 except the use of 8.2 g of the liquid crystal polyester (same as inEXAMPLE 52) and 73.5 g of the fluorine-containing elastomer withhydroxyl group obtained in EXAMPLE 36, to give test pieces. The tensiletest and measurements of melt flow rate and hardness (Shore hardness A)were carried out. The results are shown in TABLE 18.

EXAMPLE 66

A thermoplastic elastomer composition prepared by melt-blending thefluorine-containing elastomer with hydroxyl group and the liquid crystalpolyester

Kneading and molding were carried out in the same manner as in EXAMPLE65 except the use of the fluorine-containing elastomer with hydroxylgroup obtained in EXAMPLE 38, to give test pieces. The results are shownin TABLE 18.

EXAMPLE 67

A thermoplastic elastomer composition prepared by melt-blending thefluorine-containing elastomer with hydroxyl group and the liquid crystalpolyester

Kneading and molding were carried out in the same manner as in EXAMPLE65 except the use of 10.7 g of the liquid crystal polyester (same as inEXAMPLE 52) and 60.6 g of the fluorine-containing elastomer withhydroxyl group obtained in EXAMPLE 38, to give test pieces. The resultsare shown in TABLE 18.

EXAMPLE 68

A thermoplastic elastomer composition prepared by melt-blending thefluorine-containing elastomer having hydroxyl group and the liquidcrystal polyester

Kneading and molding were carried out in the same manner as in EXAMPLE65 except the use of 13.9 g of the liquid crystal polyester (same as inEXAMPLE 52) and 55.9 g of the fluorine-containing elastomer withhydroxyl group obtained in EXAMPLE 38, to give test pieces. The resultsare shown in TABLE 18.

COMPARATIVE EXAMPLES 21 TO 23

Kneading and molding were carried out in the same manner as in EXAMPLE65 for COMPARATIVE EXAMPLE 21, in EXAMPLE 67 for COMPARATIVE EXAMPLE 22,and in EXAMPLE 68 for COMPARATIVE EXAMPLE 23, respectively except thatthe fluorine-containing elastomer without functional group (same as inCOMPARATIVE EXAMPLE 3) was used instead of the fluorine-containingelastomer with hydroxyl group, to give test pieces. The results areshown in TABLE 18.

Also FIG. 6 shows stress-strain curves in the tensile test of the moldedarticles obtained in EXAMPLES 66 to 68 and COMPARATIVE EXAMPLE 22.

                                      TABLE 18                                    __________________________________________________________________________                                  Com. Com. Com.                                  Test Results  Ex. 65                                                                            Ex. 66                                                                            Ex. 67                                                                            Ex. 68                                                                            Ex. 21                                                                             Ex. 22                                                                             Ex. 23                                __________________________________________________________________________    Composition (% by weight)                                                     Fluorine-containing polymer (D)                                               with functional group                                                         Polymer of EXAMPLE 36                                                                       90  --  --  --  --   --   --                                    Polymer of EXAMPLE 38                                                                       --  90  85  80  --   --   --                                    Thermoplastic resin (E)                                                       Liquid crystal polyester (I).sup.1)                                                         10  10  15  20  10   15   20                                    Fluorine-containing polymer (F)                                               without functional group                                                      VdF/TFE/HFP copolymer.sup.2)                                                                --  --  --  --  90   85   80                                    (elastomer)                                                                   Properties of composition                                                     (Tensile test).sup.3)                                                         Tensile strength (kgf/cm.sup.2)                                                             41.6                                                                              51.4                                                                              56.4                                                                              62.4                                                                              (6.3).sup.4)                                                                       (5.7)                                                                              (7.5)                                 Elongation (%)                                                                              405 530 390 210 Cannot be                                                                          Cannot be                                                                          Cannot be                                                           fixed.sup.5)                                                                       fixed                                                                              fixed                                 Melt flow rate.sup.6) (g/10 min)                                                            3.56                                                                              9.90                                                                              20.2                                                                              39.1                                                                              --   --   --                                    Hardness (HsA)                                                                              56  55  72  83  40   44   62                                    __________________________________________________________________________     .sup.1) NOVACCURATE E310 available from Mitsubishi Chemical Corp.             .sup.2) DMEL G902 available from Daikin Industries, Ltd.                      .sup.3) Crosshead speed 10 mm/min.                                            .sup.4) Strength at maximum point                                             .sup.5) No breakage occurred because of low stress against elongation         .sup.6) At 250° C. under 20 kgf/cm.sup.2 load                     

As it is clear from TABLE 18 and FIG. 6, the compositions (EXAMPLES 65,66, 67 and 68) obtained by melt-blending the fluorine-containingelastomer with hydroxyl group and the liquid crystal polyester in thespecific composition range exhibits a high stress against elongation andhave properties like a crosslinked rubber. Further the compositionsprepared by blending the fluorine-containing elastomer with hydroxylgroup and the liquid crystal polyester exhibit high temperatureflowability and thus have characteristics as a thermoplastic elastomer.

Also the thermoplastic elastomers having various hardnesses can beprepared by selecting a ratio of the fluorine-containing elastomer withhydroxyl group to the liquid crystal polyester from the specificcomposition range.

On the contrary, the compositions (COMPARATIVE EXAMPLES 21, 22 and 23)prepared by blending with the fluorine-containing elastomer withoutfunctional group are merely blended compositions of an unvulcanizedrubber and the liquid crystal polyester, and therefore exhibitflowability at high temperature but only low stress against elongationand has no rubber elasticity.

EXAMPLE 69

Addition of the fluorine-containing polymer with functional group whenpolycarbonate and ETFE are blended.

A Brabender mixer being set at 290° C. was charged with 31.3 g ofpolycarbonate (PANLITE L-1225WP available from Teijin Chemicals Ltd.),and after melting at 10 rpm for 2 minutes, 7.2 g of ETFE (same as inEXAMPLE 50) was added and mixed for 2 minutes. Then 1. 5 g of thefluorine-containing polymer with hydroxyl group of EXAMPLE 19 was addedat 50 rpm, followed by kneading at 100 rpm for 5 minutes.

The obtained composition was compression-molded at 29° C. to preparetest pieces, and the tensile test and solvent resistance test werecarried out.

The solvent resistance test was conducted in the following manner.

(Solvent resistance test)

The test piece was dipped in toluene and then put in a bath maintainingat a constant temperature and allowed to stand at 25° C. for 48 hours.The volume change of the molded article after the test was measured.

The results are shown in TABLE 19.

COMPARATIVE EXAMPLE 24

A Brabender mixer being set at 290° C. was charged with 37.6 g ofpolycarbonate (same as in EXAMPLE 69), and after melting at 10 rpm for 2minutes, 16.1 g of ETFE (same as in EXAMPLE 50) was added at 50 rpm,followed by kneading at 100 rpm. The test pieces were prepared in thesame manner as in EXAMPLE 69. The results are shown in TABLE 19.

COMPARATIVE EXAMPLE 25

Molding was carried out in the same manner as in EXAMPLE 69 by usingpolycarbonate (same as in EXAMPLE 69) to prepare test pieces. Theresults are shown in TABLE 19.

                  TABLE 19                                                        ______________________________________                                                                  Com.     Com.                                       Test Results    Ex. 69    Ex. 24   Ex. 25                                     ______________________________________                                        Composition (% by weight)                                                     Fluorine containing polymer (D)                                                                5        --       --                                         with functional group                                                         Polymer of EXAMPLE 19                                                         Thermoplastic resin (E)                                                                       70        70       100                                        Polycarbonate                                                                 Fluorine containing polymer                                                                   25        30        0                                         without functional group                                                      ETFE.sup.1)                                                                   Properties of composition                                                     (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                               425       419      670                                        Tensile modulus (kgf/cm.sup.2)                                                                13300     10700    13100                                      (Solvent resistance test).sup.2)                                                              25        47       58                                         Volume change (%)                                                             ______________________________________                                         .sup.1) NEOFLON ETFE, EP610 available from Daikin Industries, Ltd.            .sup.2) 48hour dipping in toluene at 25° C.                       

As it is clear from the results of TABLE 19, as compared with the simpleblend of polycarbonate and ETFE, solvent resistance of polycarbonate canbe effectively improved without lowering mechanical properties by addingthe fluorine-containing polymer with hydroxyl group when blendingpolycarbonate and ETFE.

EXAMPLE 70

A 60 cm³ Brabender mixer being set at 370° C. was charged with 39.0 g ofthe liquid crystal polyester (same as in EXAMPLE 62), and after meltingat 10 rpm for 3 minutes, 39.0 g of the fluorine-containing polymer withhydroxyl group obtained in EXAMPLE 35 was added at 50 rpm, followed byfurther kneading at 100 rpm for 5 minutes.

The obtained composition was crushed, and test pieces was prepared by aninjection molding machine at a cylinder temperature of 320° to 360° C.and a die temperature of 190° C. Then measurements of shrinkage frommold dimensions, tensile test and bending test were carried out. Theresults are shown in TABLE 20.

COMPARATIVE EXAMPLE 26

Kneading and molding were carried out in the same manner as in EXAMPLE70 except that PFA (same as in EXAMPLE 62) was used instead of thefluorine-containing polymer with hydroxyl group, to give test pieces.The results are shown in TABLE 20.

                  TABLE 20                                                        ______________________________________                                                                     Com.                                             Test Results        Ex. 70   Ex. 26                                           ______________________________________                                        Composition (% by weight)                                                     Fluorine-containing polymer (D)                                                                   50       --                                               with functional group                                                         Polymer of EXAMPLE 35                                                         Thermoplastic resin (E)                                                                           50       50                                               Liquid crystal polyester (IV).sup.1)                                          Fluorine-containing polymer (F)                                                                   --       50                                               without functional group                                                      PFA.sup.2)                                                                    Properties of composition                                                     (Shrinkage from mold dimensions)                                              Flow direction (%)     0.14     0.11                                          Direction vertical to flow (%)                                                                       2.71     2.43                                          (Tensile test)                                                                Tensile strength (kgf/cm.sup.2)                                                                   1080     660                                              Tensile modulus (kgf/cm.sup.2)                                                                    52100    43700                                            (Bending test)                                                                Bending strength (kgf/cm.sup.2)                                                                   625      365                                              Bending modulus (kgf/cm.sup.2)                                                                    42000    46600                                            ______________________________________                                         .sup.1) SUMIKA SUPER LCP E6000 available from Sumitomo Chemical Co., Ltd.     .sup.2) NEOFLON PFA AP201 available from Daikin Industries, Ltd.         

INDUSTRIAL APPLICABILITY

The fluorine-containing polymer with functional group which is preparedby polymerizing the fluorine-containing olefin with functional group ofthe present invention has good affinity with various heat-resistingthermoplastic resins to form homogeneous dispersion.

Further the molded articles prepared by molding the thermoplastic resincomposition comprising the above-mentioned polymer and thermoplasticresin have excellent mechanical properties, moldability, thermalresistance and chemical resistance.

We claim:
 1. A fluorine-containing olefin represented by the formula(IV):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.6 --(CH.sub.2).sub.k --X.sup.2 (IV)

wherein X² is ##STR77## R_(f) ⁶ is a fluorine-substituted alkylene grouphaving 1 to 40 carbon atoms or --OR_(f) ⁷ --(R_(f) ⁷ is afluorine-substituted fluorine-containing alkylene group having 1 to 40carbon atoms or a fluorine-substituted fluorine-containing ether grouphaving 3 to 50 carbon atoms), k is 0 or an integer of 1 to
 6. 2. Afluorine-containing olefin represented by the formula (V):

    CH.sub.2 ═CFCF.sub.2 --R.sub.f.sup.8 --(CH.sub.2).sub.m --COOR.sup.4 (V)

wherein R⁴ is H, an alkyl group having 1 to 6 carbon atoms, Na, K, Li orNH₄, R_(f) ⁸ is a fluorine-substituted alkylene group having 3 to 40carbon atoms or --OR_(f) ⁹ -- (R_(f) ⁹ is a fluorine-substitutedalkylene group having 2 to 40 carbon atoms or a fluorine-substitutedether group having 3 to 50 carbon atoms), m is 0 or an integer of 1 to6.
 3. The fluorine-containing olefin of claim 1, wherein said X² is--CH₂ OH.
 4. The fluorine-containing olefin of claim 1, wherein said X²is ##STR78## .
 5. The fluorine-containing olefin of claim 1, whereinsaid --R_(f) ⁶ -- is --CF₂ --(CF₂ CF₂)-- (n is 0 or an integer of 1 to10).
 6. The fluorine-containing olefin of claim 1, wherein said --R_(f)⁶ -- is ##STR79## (A³ is ##STR80## B³ is CF₃ or F, p is 0 or an integerof 1 to 5, q is 0 or an integer of 1 to 10) and k is 0 and X² is##STR81## .
 7. The fluorine-containing olefin of claim 2, wherein saidR⁴ is H.
 8. The fluorine-containing olefin of claim 2, wherein said R⁴is NH₄.
 9. The fluorine-containing olefin of claim 2, wherein said--R_(f) ⁸ -- is --CF₂ --(CF₂ CF₂)_(r) -- (r is an integer of 1 to 10).10. The fluorine-containing olefin of claim 2, wherein said --R_(f) ⁸ --is ##STR82## (A⁴ is ##STR83## B⁴ is CF₃ or F, s is 0 or an integer of 1to 5, t is 0 or an integer of 1 to 10, B⁴ is CF₃ in case of r=s=0) and mis 0.